Pre-Service Chemistry Teachers' Competencies in the Laboratory: A Cross-Grade Study in Solution Preparation

Science.gov (United States)

Karatas, F. O.

2016-01-01

One of the prerequisites for chemistry teacher candidates is to demonstrate certain laboratory skills. This article aims to determine and discuss the competencies of pre-service chemistry teachers in a chemistry laboratory context working with solution chemistry content. The participants in this study consisted of a group of pre-service chemistry…

Data assimilation in atmospheric chemistry models: current status and future prospects for coupled chemistry meteorology models

OpenAIRE

M. Bocquet; H. Elbern; H. Eskes; M. Hirtl; R. Žabkar; G. R. Carmichael; J. Flemming; A. Inness; M. Pagowski; J. L. Pérez Camaño; P. E. Saide; R. San Jose; M. Sofiev; J. Vira; A. Baklanov

2015-01-01

Data assimilation is used in atmospheric chemistry models to improve air quality forecasts, construct re-analyses of three-dimensional chemical (including aerosol) concentrations and perform inverse modeling of input variables or model parameters (e.g., emissions). Coupled chemistry meteorology models (CCMM) are atmospheric chemistry models that simulate meteorological processes and chemical transformations jointly. They offer the possibility to assimilate both meteorologica...

Multi-Scale Modeling of the Gamma Radiolysis of Nitrate Solutions.

Science.gov (United States)

Horne, Gregory P; Donoclift, Thomas A; Sims, Howard E; Orr, Robin M; Pimblott, Simon M

2016-11-17

A multiscale modeling approach has been developed for the extended time scale long-term radiolysis of aqueous systems. The approach uses a combination of stochastic track structure and track chemistry as well as deterministic homogeneous chemistry techniques and involves four key stages: radiation track structure simulation, the subsequent physicochemical processes, nonhomogeneous diffusion-reaction kinetic evolution, and homogeneous bulk chemistry modeling. The first three components model the physical and chemical evolution of an isolated radiation chemical track and provide radiolysis yields, within the extremely low dose isolated track paradigm, as the input parameters for a bulk deterministic chemistry model. This approach to radiation chemical modeling has been tested by comparison with the experimentally observed yield of nitrite from the gamma radiolysis of sodium nitrate solutions. This is a complex radiation chemical system which is strongly dependent on secondary reaction processes. The concentration of nitrite is not just dependent upon the evolution of radiation track chemistry and the scavenging of the hydrated electron and its precursors but also on the subsequent reactions of the products of these scavenging reactions with other water radiolysis products. Without the inclusion of intratrack chemistry, the deterministic component of the multiscale model is unable to correctly predict experimental data, highlighting the importance of intratrack radiation chemistry in the chemical evolution of the irradiated system.

Fluctuation theory of solutions applications in chemistry, chemical engineering, and biophysics

CERN Document Server

Smith, Paul E

2013-01-01

There are essentially two theories of solutions that can be considered exact: the McMillan-Mayer theory and Fluctuation Solution Theory (FST). The first is mostly limited to solutes at low concentrations, while FST has no such issue. It is an exact theory that can be applied to any stable solution regardless of the number of components and their concentrations, and the types of molecules and their sizes. Fluctuation Theory of Solutions: Applications in Chemistry, Chemical Engineering, and Biophysics outlines the general concepts and theoretical basis of FST and provides a range of applications

Containment Sodium Chemistry Models in MELCOR.

Energy Technology Data Exchange (ETDEWEB)

Louie, David [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Humphries, Larry L. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Denman, Matthew R [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2017-04-01

To meet regulatory needs for sodium fast reactors’ future development, including licensing requirements, Sandia National Laboratories is modernizing MELCOR, a severe accident analysis computer code developed for the U.S. Nuclear Regulatory Commission (NRC). Specifically, Sandia is modernizing MELCOR to include the capability to model sodium reactors. However, Sandia’s modernization effort primarily focuses on the containment response aspects of the sodium reactor accidents. Sandia began modernizing MELCOR in 2013 to allow a sodium coolant, rather than water, for conventional light water reactors. In the past three years, Sandia has been implementing the sodium chemistry containment models in CONTAIN-LMR, a legacy NRC code, into MELCOR. These chemistry models include spray fire, pool fire and atmosphere chemistry models. Only the first two chemistry models have been implemented though it is intended to implement all these models into MELCOR. A new package called “NAC” has been created to manage the sodium chemistry model more efficiently. In 2017 Sandia began validating the implemented models in MELCOR by simulating available experiments. The CONTAIN-LMR sodium models include sodium atmosphere chemistry and sodium-concrete interaction models. This paper presents sodium property models, the implemented models, implementation issues, and a path towards validation against existing experimental data.

Solving vertical transport and chemistry in air pollution models

International Nuclear Information System (INIS)

Berkvens, P.J.F.; Botchev, M.A.; Verwer, J.G.; Krol, M.C.; Peters, W.

2000-01-01

For the time integration of stiff transport-chemistry problems from air pollution modelling, standard ODE solvers are not feasible due to the large number of species and the 3D nature. The popular alternative, standard operator splitting, introduces artificial transients for short-lived species. This complicates the chemistry solution, easily causing large errors for such species. In the framework of an operational global air pollution model, we focus on the problem formed by chemistry and vertical transport, which is based on diffusion, cloud-related vertical winds, and wet deposition. Its specific nature leads to full Jacobian matrices, ruling out standard implicit integration. We compare Strang operator splitting with two alternatives: source splitting and an (unsplit) Rosenbrock method with approximate matrix factorization, all having equal computational cost. The comparison is performed with real data. All methods are applied with half-hour time steps, and give good accuracies. Rosenbrock is the most accurate, and source splitting is more accurate than Strang splitting. Splitting errors concentrate in short-lived species sensitive to solar radiation and species with strong emissions and depositions. 30 refs

Chemistry in high temperature aqueous solutions application to the power industry

International Nuclear Information System (INIS)

Cohen, P.

1990-01-01

The power industry utilizes water (aqueous solutions) for two main functions: as a medium for heat transfer and transport and as a thermodynamic working fluid. These functions are performed in systems fabricated from a wide variety of materials, over a wide range of thermal and hydraulic conditions, and at medium temperatures and densities which determine the significant chemical properties. The major chemical interest is in the concentrated solutions derived from the dilute working fluid at selected sites defined by the physical arrangement and temperature and in their consequential effects on heat transfer and corrosion. Examples of these sites for typical fossil fired and nuclear steam generating equipment are described, as well as the extent and limit of the concentration process. The history of steam power plant water chemistry is discussed from the point of view of the chemical processes involved. The period covered is from the 1920s to the present state of the art, which is a major application of the subject of this symposium--chemistry in high temperature aqueous solution

Modeling the atmospheric chemistry of TICs

Science.gov (United States)

Henley, Michael V.; Burns, Douglas S.; Chynwat, Veeradej; Moore, William; Plitz, Angela; Rottmann, Shawn; Hearn, John

2009-05-01

An atmospheric chemistry model that describes the behavior and disposition of environmentally hazardous compounds discharged into the atmosphere was coupled with the transport and diffusion model, SCIPUFF. The atmospheric chemistry model was developed by reducing a detailed atmospheric chemistry mechanism to a simple empirical effective degradation rate term (keff) that is a function of important meteorological parameters such as solar flux, temperature, and cloud cover. Empirically derived keff functions that describe the degradation of target toxic industrial chemicals (TICs) were derived by statistically analyzing data generated from the detailed chemistry mechanism run over a wide range of (typical) atmospheric conditions. To assess and identify areas to improve the developed atmospheric chemistry model, sensitivity and uncertainty analyses were performed to (1) quantify the sensitivity of the model output (TIC concentrations) with respect to changes in the input parameters and (2) improve, where necessary, the quality of the input data based on sensitivity results. The model predictions were evaluated against experimental data. Chamber data were used to remove the complexities of dispersion in the atmosphere.

The radiation chemistry of aqueous sodium terephthalate solutions

International Nuclear Information System (INIS)

Matthews, R.W.

1980-04-01

The radiation chemistry of cobalt-60 gamma-irradiated aqueous sodium terephthalate solutions has been studied. In aerated 4 x 10 -4 M sodium hydroxide solutions, the main products are hydroxyterephthalate (HTA) (G = 0.99 +- 0.01), carbonate (G = 1.31 +- 0.08), and peroxides (G = 2.84 +- 0.04). The HTA and carbonate species are both formed as a result of hydroxyl radical attack and account for approximately 90 per cent of hydroxyl radical reactions. Oxygen needs to be present for efficient conversion of the terephthalate-OH radical adduct to HTA and oxygenation increases G(HTA) above the aerated solution value. G(HTA) is unaffected by changes in terephthalate concentration between 1 x 10 -4 M and 1 x 10 -2 M in sodium hydroxide solutions at pH 10. Decreasing the solution pH does however affect G(HTA). In phosphate buffered solutions pH 6.85, G(HTA) is 0.93 +- 0.01 and lower values are obtained with further decrease in solution pH. The lowering of the G(HTA) value is attributed to recombination reactions between the terephthalate-OH radical products and reducing radical products. Experimental evidence supporting the recombination postulate was obtained from the measurement of a parallel decrease in the peroxide yield and the observation of a dose rate effect on G(HTA). Competition kinetic studies with the added solutes carbonate and bicarbonate gave the rate ratios k (OH + TA 2- ) : k(OH + CO 3 2- ) : k(OH + HCO 3 - ) = 1 : 0.105 : 0.0036

Impacts of operating conditions and solution chemistry on osmotic membrane structure and performance

KAUST Repository

Wong, Mavis C.Y.; Martinez, Kristina; Ramon, Guy Z.; Hoek, Eric M.V.

2012-01-01

Herein, we report on changes in the performance of a commercial cellulose triacetate (CTA) membrane, imparted by varied operating conditions and solution chemistries. Changes to feed and draw solution flow rate did not significantly alter the CTA membrane's water permeability, salt permeability, or membrane structural parameter when operated with the membrane skin layer facing the draw solution (PRO-mode). However, water and salt permeability increased with increasing feed or draw solution temperature, while the membrane structural parameter decreased with increasing draw solution, possibly due to changes in polymer intermolecular interactions. High ionic strength draw solutions may de-swell the CTA membrane via charge neutralization, which resulted in lower water permeability, higher salt permeability, and lower structural parameter. This observed trend was further exacerbated by the presence of divalent cations which tends to swell the polymer to a greater extent. Finally, the calculated CTA membrane's structural parameter was lower and less sensitive to external factors when operated in PRO-mode, but highly sensitive to the same factors when the skin layer faced the feed solution (FO-mode), presumably due to swelling/de-swelling of the saturated porous substructure by the draw solution. This is a first attempt aimed at systematically evaluating the changes in performance of the CTA membrane due to operating conditions and solution chemistry, shedding new insight into the possible advantages and disadvantages of this material in certain applications. © 2011 Elsevier B.V.

Impacts of operating conditions and solution chemistry on osmotic membrane structure and performance

KAUST Repository

Wong, Mavis C.Y.

2012-02-01

Herein, we report on changes in the performance of a commercial cellulose triacetate (CTA) membrane, imparted by varied operating conditions and solution chemistries. Changes to feed and draw solution flow rate did not significantly alter the CTA membrane\\'s water permeability, salt permeability, or membrane structural parameter when operated with the membrane skin layer facing the draw solution (PRO-mode). However, water and salt permeability increased with increasing feed or draw solution temperature, while the membrane structural parameter decreased with increasing draw solution, possibly due to changes in polymer intermolecular interactions. High ionic strength draw solutions may de-swell the CTA membrane via charge neutralization, which resulted in lower water permeability, higher salt permeability, and lower structural parameter. This observed trend was further exacerbated by the presence of divalent cations which tends to swell the polymer to a greater extent. Finally, the calculated CTA membrane\\'s structural parameter was lower and less sensitive to external factors when operated in PRO-mode, but highly sensitive to the same factors when the skin layer faced the feed solution (FO-mode), presumably due to swelling/de-swelling of the saturated porous substructure by the draw solution. This is a first attempt aimed at systematically evaluating the changes in performance of the CTA membrane due to operating conditions and solution chemistry, shedding new insight into the possible advantages and disadvantages of this material in certain applications. © 2011 Elsevier B.V.

Molecular Twister: A Game for Exploring Solution Chemistry †

OpenAIRE

Masonjones, Sawyer R.; Masonjones, Heather D.; Malone, Megan C.; Williams, Ann H.; Beemer, Margaret M.; Waggett, Rebecca J.

2014-01-01

pH is an essential biological concept with critical importance at various scales, from the molecular level, dealing with blood buffers, homeostasis, and proton gradients, all the way up to the ecosystem level, with soil chemistry and acid rain. However, pH is also a concept that spawns student misconceptions and misunderstanding in terms of what is happening in a solution on the atomic level. The Molecular Twister game, created for a Florida Department of Education funded professional develop...

Modelling stratospheric chemistry in a global three-dimensional chemical transport model

Energy Technology Data Exchange (ETDEWEB)

Rummukainen, M [Finnish Meteorological Inst., Sodankylae (Finland). Sodankylae Observatory

1996-12-31

Numerical modelling of atmospheric chemistry aims to increase the understanding of the characteristics, the behavior and the evolution of atmospheric composition. These topics are of utmost importance in the study of climate change. The multitude of gases and particulates making up the atmosphere and the complicated interactions between them affect radiation transfer, atmospheric dynamics, and the impacts of anthropogenic and natural emissions. Chemical processes are fundamental factors in global warming, ozone depletion and atmospheric pollution problems in general. Much of the prevailing work on modelling stratospheric chemistry has so far been done with 1- and 2-dimensional models. Carrying an extensive chemistry parameterisation in a model with high spatial and temporal resolution is computationally heavy. Today, computers are becoming powerful enough to allow going over to 3-dimensional models. In order to concentrate on the chemistry, many Chemical Transport Models (CTM) are still run off-line, i.e. with precalculated and archived meteorology and radiation. In chemistry simulations, the archived values drive the model forward in time, without interacting with the chemical evolution. This is an approach that has been adopted in stratospheric chemistry modelling studies at the Finnish Meteorological Institute. In collaboration with the University of Oslo, a development project was initiated in 1993 to prepare a stratospheric chemistry parameterisation, fit for global 3-dimensional modelling. This article presents the parameterisation approach. Selected results are shown from basic photochemical simulations

Modelling stratospheric chemistry in a global three-dimensional chemical transport model

Energy Technology Data Exchange (ETDEWEB)

Rummukainen, M. [Finnish Meteorological Inst., Sodankylae (Finland). Sodankylae Observatory

1995-12-31

Numerical modelling of atmospheric chemistry aims to increase the understanding of the characteristics, the behavior and the evolution of atmospheric composition. These topics are of utmost importance in the study of climate change. The multitude of gases and particulates making up the atmosphere and the complicated interactions between them affect radiation transfer, atmospheric dynamics, and the impacts of anthropogenic and natural emissions. Chemical processes are fundamental factors in global warming, ozone depletion and atmospheric pollution problems in general. Much of the prevailing work on modelling stratospheric chemistry has so far been done with 1- and 2-dimensional models. Carrying an extensive chemistry parameterisation in a model with high spatial and temporal resolution is computationally heavy. Today, computers are becoming powerful enough to allow going over to 3-dimensional models. In order to concentrate on the chemistry, many Chemical Transport Models (CTM) are still run off-line, i.e. with precalculated and archived meteorology and radiation. In chemistry simulations, the archived values drive the model forward in time, without interacting with the chemical evolution. This is an approach that has been adopted in stratospheric chemistry modelling studies at the Finnish Meteorological Institute. In collaboration with the University of Oslo, a development project was initiated in 1993 to prepare a stratospheric chemistry parameterisation, fit for global 3-dimensional modelling. This article presents the parameterisation approach. Selected results are shown from basic photochemical simulations

Physico-chemistry of actinides and other radioelements in solutions and at the interfaces

International Nuclear Information System (INIS)

2000-01-01

This document provides the 61 papers (transparencies used during the presentations and posters) presented at the 1999 PRACTIS days, held February 17-18, 2000 in Villeneuve-les-Avignon. The content comprises 9 conferences dealing with 1)simulation of solvation, coordination and liquid-liquid extraction of rare earth and uranyl cations 2)overview on the complexation selectivity of actinides(III) and rare earths(III) by aromatic poly-nitrogenous ligands 3)detection, characterization and interaction between supramolecular aggregates of extractants: macroscopic consequences on the stability and on the macroscopic behaviour 4)chemistry of technetium in reducing medium: application to researches on radioactive waste management 5) separations by pyro-chemistry (CEA program) 6)overview on the Goethite operation 7)use of time-resolved luminescence spectroscopy to the determination of sorption sites at the interfaces 8)dissolution of uranium dioxide in an argillaceous water: results in oxidizing and reducing conditions 9)treatment and storage of radioactive wastes from weapon-grade plutonium production in Russia and other countries. A large part of the conference was devoted to poster sessions on the following topics: physico-chemistry in homogeneous solutions (22 posters), transfer kinetics of actinides and rare earths between liquid phases and separations (9 posters), physico-chemistry of the solid-solution interface (9 posters), simulation and molecular dynamics (5 posters), uranium dioxide and other oxides (1 poster), long-lived fission products (6 posters). (O.M.)

Scientific Approach and Inquiry Learning Model in the Topic of Buffer Solution: A Content Analysis

Science.gov (United States)

Kusumaningrum, I. A.; Ashadi, A.; Indriyanti, N. Y.

2017-09-01

Many concepts in buffer solution cause student’s misconception. Understanding science concepts should apply the scientific approach. One of learning models which is suitable with this approach is inquiry. Content analysis was used to determine textbook compatibility with scientific approach and inquiry learning model in the concept of buffer solution. By using scientific indicator tools (SIT) and Inquiry indicator tools (IIT), we analyzed three chemistry textbooks grade 11 of senior high school labeled as P, Q, and R. We described how textbook compatibility with scientific approach and inquiry learning model in the concept of buffer solution. The results show that textbook P and Q were very poor and book R was sufficient because the textbook still in procedural level. Chemistry textbooks used at school are needed to be improved in term of scientific approach and inquiry learning model. The result of these analyses might be of interest in order to write future potential textbooks.

Solution chemistry

Energy Technology Data Exchange (ETDEWEB)

None

1973-07-01

Research progress is reported on studies in heavy element chemistry. Topics considered are: synergistic complexes of plutonyl ion; water uptake in synergistic systems; formation constants of some uranyl BETA -diketone complexes; thermodynamic acid dissociation constants of BETA -diketones; thermodynamic formation constants of uranyl BETA -diketonates; thiocyanate complexes of some trivalent lanthanides and actinides; stability constants of actinide complexes using dinonyl naphthalenesulfonic acid extraction; TBP extraction of actinides; stability constants of complexes of Pu(III) with 5- sulfosalicycllc acid; and solvent extraction behavior of Pu( VII). (DHM)

On the use of mass-conserving wind fields in chemistry-transport models

Directory of Open Access Journals (Sweden)

B. Bregman

2003-01-01

Full Text Available A new method has been developed that provides mass-conserving wind fields for global chemistry-transport models. In previous global Eulerian modeling studies a mass-imbalance was found between the model mass transport and the surface pressure tendencies. Several methods have been suggested to correct for this imbalance, but so far no satisfactory solution has been found. Our new method solves these problems by using the wind fields in a spherical harmonical form (divergence and vorticity by mimicing the physics of the weather forecast model as closely as possible. A 3-D chemistry-transport model was used to show that the calculated ozone fields with the new processing method agree remarkably better with ozone observations in the upper troposphere and lower stratosphere. In addition, the calculated age of air in the lower stratosphere show better agreement with observations, although the air remains still too young in the extra-tropical stratosphere.

Equilibrium and kinetic models for colloid release under transient solution chemistry conditions.

Science.gov (United States)

Bradford, Scott A; Torkzaban, Saeed; Leij, Feike; Simunek, Jiri

2015-10-01

We present continuum models to describe colloid release in the subsurface during transient physicochemical conditions. Our modeling approach relates the amount of colloid release to changes in the fraction of the solid surface area that contributes to retention. Equilibrium, kinetic, equilibrium and kinetic, and two-site kinetic models were developed to describe various rates of colloid release. These models were subsequently applied to experimental colloid release datasets to investigate the influence of variations in ionic strength (IS), pH, cation exchange, colloid size, and water velocity on release. Various combinations of equilibrium and/or kinetic release models were needed to describe the experimental data depending on the transient conditions and colloid type. Release of Escherichia coli D21g was promoted by a decrease in solution IS and an increase in pH, similar to expected trends for a reduction in the secondary minimum and nanoscale chemical heterogeneity. The retention and release of 20nm carboxyl modified latex nanoparticles (NPs) were demonstrated to be more sensitive to the presence of Ca(2+) than D21g. Specifically, retention of NPs was greater than D21g in the presence of 2mM CaCl2 solution, and release of NPs only occurred after exchange of Ca(2+) by Na(+) and then a reduction in the solution IS. These findings highlight the limitations of conventional interaction energy calculations to describe colloid retention and release, and point to the need to consider other interactions (e.g., Born, steric, and/or hydration forces) and/or nanoscale heterogeneity. Temporal changes in the water velocity did not have a large influence on the release of D21g for the examined conditions. This insensitivity was likely due to factors that reduce the applied hydrodynamic torque and/or increase the resisting adhesive torque; e.g., macroscopic roughness and grain-grain contacts. Our analysis and models improve our understanding and ability to describe the amounts

Integrated modeling and characterization of local crack chemistry

International Nuclear Information System (INIS)

Savchik, J.A.; Burke, M.S.

1996-01-01

The MULTEQ computer program has become an industry wide tool which can be used to calculate the chemical composition in a flow occluded region as the solution within concentrates due to a local boiling process. These results can be used to assess corrosion concerns in plant equipment such as steam generators. Corrosion modeling attempts to quantify corrosion assessments by accounting for the mass transport processes involved in the corrosion mechanism. MULTEQ has played an ever increasing role in defining the local chemistry for such corrosion models. This paper will outline how the integration of corrosion modeling with the analysis of corrosion films and deposits can lead to the development of a useful modeling tool, wherein MULTEQ is interactively linked to a diffusion and migration transport process. This would provide a capability to make detailed inferences of the local crack chemistry based on the analyses of the local corrosion films and deposits inside a crack and thus provide guidance for chemical fixes to avoid cracking. This methodology is demonstrated for a simple example of a cracked tube. This application points out the utility of coupling MULTEQ with a mass transport process and the feasibility of an option in a future version of MULTEQ that would permit relating film and deposit analyses to the local chemical environment. This would increase the amount of information obtained from removed tube analyses and laboratory testing that can contribute to an overall program for mitigating tubing and crevice corrosion

Integrated modeling and characterization of local crack chemistry

International Nuclear Information System (INIS)

Savchik, J.A.; Burke, M.S.

1995-01-01

The MULTEQ computer program has become an industry wide tool which can be used to calculate the chemical composition in a flow occluded region as the solution within concentrates due to a local boiling process. These results can be used to assess corrosion concerns in plant equipment such as steam generators. Corrosion modeling attempts to quantify corrosion assessments by accounting for the mass transport processes involved in the corrosion mechanism. MULTEQ has played an ever increasing role in defining the local chemistry for such corrosion models. This paper will outline how the integration of corrosion modeling with the analysis of corrosion films and deposits can lead to the development of a useful modeling tool, wherein MULTEQ is interactively linked to a diffusion and migration transport process. This would provide a capability to make detailed inferences of the local crack chemistry based on the analyses of the local corrosion films and deposits inside a crack and thus provide guidance for chemical fixes to avoid cracking. This methodology is demonstrated for a simple example of a cracked tube. This application points out the utility of coupling MULTEQ with a mass transport process and the feasibility of an option in a future version of MULTEQ that would permit relating film and deposit analyses to the local chemical environment. This would increase the amount of information obtained from removed tube analyses and laboratory testing that can contribute to an overall program for mitigating tubing and crevice corrosion

Quantifying atmospheric transport, chemistry, and mixing using a new trajectory-box model and a global atmospheric-chemistry GCM

Directory of Open Access Journals (Sweden)

H. Riede

2009-12-01

Full Text Available We present a novel method for the quantification of transport, chemistry, and mixing along atmospheric trajectories based on a consistent model hierarchy. The hierarchy consists of the new atmospheric-chemistry trajectory-box model CAABA/MJT and the three-dimensional (3-D global ECHAM/MESSy atmospheric-chemistry (EMAC general circulation model. CAABA/MJT employs the atmospheric box model CAABA in a configuration using the atmospheric-chemistry submodel MECCA (M, the photochemistry submodel JVAL (J, and the new trajectory submodel TRAJECT (T, to simulate chemistry along atmospheric trajectories, which are provided offline. With the same chemistry submodels coupled to the 3-D EMAC model and consistent initial conditions and physical parameters, a unique consistency between the two models is achieved. Since only mixing processes within the 3-D model are excluded from the model consistency, comparisons of results from the two models allow to separate and quantify contributions of transport, chemistry, and mixing along the trajectory pathways. Consistency of transport between the trajectory-box model CAABA/MJT and the 3-D EMAC model is achieved via calculation of kinematic trajectories based on 3-D wind fields from EMAC using the trajectory model LAGRANTO. The combination of the trajectory-box model CAABA/MJT and the trajectory model LAGRANTO can be considered as a Lagrangian chemistry-transport model (CTM moving isolated air parcels. The procedure for obtaining the necessary statistical basis for the quantification method is described as well as the comprehensive diagnostics with respect to chemistry.

The quantification method presented here allows to investigate the characteristics of transport, chemistry, and mixing in a grid-based 3-D model. The analysis of chemical processes within the trajectory-box model CAABA/MJT is easily extendable to include, for example, the impact of different transport pathways or of mixing processes onto

Radiation chemistry

Energy Technology Data Exchange (ETDEWEB)

None

1973-07-01

Research progress is reported on radiation chemistry of heavy elements that includes the following topics: radiation chemistry of plutonium in nitric acid solutions (spectrophotometric analysis and gamma radiolysis of Pu(IV) and Pu(VI) in nitric acid solution); EPR studies of intermediates formed in radiolytic reactions with aqueous medium; two-phase radiolysis and its effect on the distribution coefficient of plutonium; and radiation chemistry of nitric acid. (DHM)

Modelling of the local chemistry in stagnant areas in the PWR primary circuit

International Nuclear Information System (INIS)

Reid, Rick; Fruzzetti, Keith; Ahluwalia, Al; Summe, Alex; Dame, Cecile; Schmitt, Kyle

2014-01-01

MRP-236 demonstrated a correlation between stagnant or low flow conditions and stress corrosion cracking (SCC) of stainless steel components in the PWR primary system. Of the approximately 140 SCC events documented (affecting 15 different components), 83% involved stagnant or low flow conditions that were likely to be associated with chemical environments different from the well mixed bulk coolant. The chemistry in such locations is typically not monitored, and sampling is difficult or impossible. Actions to improve chemistry in regions of low or no coolant flow, such as flushing, cycling of components and imposition of more stringent make up water chemistry controls affect both operational costs and outage schedules. Similarly, design changes to improve flow in affected areas are costly or impracticable. Improving the understanding of the factors controlling chemistry in such areas and development of the capability to predict typical and worst case conditions will allow an informed assessment of procedural actions and/or design changes to improve local chemistry and thereby reduce SCC susceptibility. A project was undertaken to develop a model to predict local chemistry conditions in stagnant locations. The model comprises the iterative application of the EPRI MULTEQ solution chemistry equilibrium code and standard thermodynamic relationships to predict local chemistry conditions considered likely to have been present at the surfaces of components when SCC was initiated. The starting chemistry conditions are based on PWR primary system chemistry from different plant maneuvers (e.g., startup and shutdown conditions). The model was applied to three example components where SCC has occurred in the field. The selected components were: control rod drive mechanism canopy seals; valve drain lines; and reactor vessel o-ring leak-off lines. This paper provides a summary of the model and predicted local chemistry conditions that develop for the three example component as a

Transport of titanium dioxide nanoparticles in saturated porous media under various solution chemistry conditions

International Nuclear Information System (INIS)

Wang Yu; Gao Bin; Morales, Verónica L.; Tian Yuan; Wu Lei; Gao Jie; Bai Wei; Yang Liuyan

2012-01-01

Because of its wide applications, nanosized titanium dioxide may become a potential environmental risk to soil and groundwater system. It is therefore important to improve current understanding of the environmental fate and transport of titanium oxides nanoparticles (TONPs). In this work, the effect of solution chemistry (i.e., pH, ionic strength, and natural organic matter (NOM) concentration) on the deposition and transport of TONPs in saturated porous media was examined in detail. Laboratory columns packed with acid-cleaned quartz sand were used in the experiment as porous media. Transport experiments were conducted with various chemistry combinations, including four ionic strengths, three pH levels, and two NOM concentrations. The results showed that TONP mobility increased with increasing solution pH, but decreased with increasing solution ionic strength. It is also found that the presence of NOM in the system enhanced the mobility of TONPs in the saturated porous media. The Derjaguin–Landau–Verwey–Overbeek (DLVO) theory was used to justify the mobility trends observed in the experimental data. Predictions from the theory agreed excellently with the experimental data.

Effects of solution chemistry and aging time on prion protein adsorption and replication of soil-bound prions.

Directory of Open Access Journals (Sweden)

Samuel E Saunders

2011-04-01

Full Text Available Prion interactions with soil may play an important role in the transmission of chronic wasting disease (CWD and scrapie. Prions are known to bind to a wide range of soil surfaces, but the effects of adsorption solution chemistry and long-term soil binding on prion fate and transmission risk are unknown. We investigated HY TME prion protein (PrP(Sc adsorption to soil minerals in aqueous solutions of phosphate buffered saline (PBS, sodium chloride, calcium chloride, and deionized water using western blotting. The replication efficiency of bound prions following adsorption in these solutions was also evaluated by protein misfolding cyclic amplification (PMCA. Aging studies investigated PrP(Sc desorption and replication efficiency up to one year following adsorption in PBS or DI water. Results indicate that adsorption solution chemistry can affect subsequent prion replication or desorption ability, especially after incubation periods of 30 d or longer. Observed effects were minor over the short-term (7 d or less. Results of long-term aging experiments demonstrate that unbound prions or prions bound to a diverse range of soil surfaces can readily replicate after one year. Our results suggest that while prion-soil interactions can vary with solution chemistry, prions bound to soil could remain a risk for transmitting prion diseases after months in the environment.

Dilution physics modeling: Dissolution/precipitation chemistry

International Nuclear Information System (INIS)

Onishi, Y.; Reid, H.C.; Trent, D.S.

1995-09-01

This report documents progress made to date on integrating dilution/precipitation chemistry and new physical models into the TEMPEST thermal-hydraulics computer code. Implementation of dissolution/precipitation chemistry models is necessary for predicting nonhomogeneous, time-dependent, physical/chemical behavior of tank wastes with and without a variety of possible engineered remediation and mitigation activities. Such behavior includes chemical reactions, gas retention, solids resuspension, solids dissolution and generation, solids settling/rising, and convective motion of physical and chemical species. Thus this model development is important from the standpoint of predicting the consequences of various engineered activities, such as mitigation by dilution, retrieval, or pretreatment, that can affect safe operations. The integration of a dissolution/precipitation chemistry module allows the various phase species concentrations to enter into the physical calculations that affect the TEMPEST hydrodynamic flow calculations. The yield strength model of non-Newtonian sludge correlates yield to a power function of solids concentration. Likewise, shear stress is concentration-dependent, and the dissolution/precipitation chemistry calculations develop the species concentration evolution that produces fluid flow resistance changes. Dilution of waste with pure water, molar concentrations of sodium hydroxide, and other chemical streams can be analyzed for the reactive species changes and hydrodynamic flow characteristics

Instructional Model and Thinking Skill in Chemistry Class

Science.gov (United States)

Langkudi, H. H.

2018-02-01

Chemistry course are considered a difficult lesson for students as evidenced by low learning outcomes on daily tests, mid-semester tests as well as final semester tests. This research intended to investigate the effect of instructional model, thinking skill and the interaction of these variables on students’ achievement in chemistry. Experimental method was applying used 2 x 2 factorial design. The results showed that the use of instructional model with thinking skill influences student’s learning outcomes, so that the chemistry teacher is recommended to pay attention to the learning model, and adjusted to the student’s skill thinking on the chemistry material being taught. The conclusion of this research is that discovery model is suitable for students who have formal thinking skill and conventional model is fit for the students that have concrete thinking skill.

Modelling the response of soil and soil solution chemistry upon roofing a forest in an area with high nitrogen deposition

Directory of Open Access Journals (Sweden)

C. van der Salm

1998-01-01

Full Text Available In the Speuld forest, the Netherlands, the dynamic soil acidification model NuCSAM has been applied to a manipulation experiment in which part of the forest was roofed to control nitrogen (N and sulphur (S deposition. The roofed area was divided into two subplots watered artificially; one received ambient N and S deposition and one with pristine N and S deposition. Concentration measurements on each plots showed a high (time-dependent spatial variability. Statistical analyses of the concentrations on both subplots showed small but significant effects of the reduction in deposition on nitrate (NO3 sulphate (SO4 and aluminum (Al concentrations. The statistical significance of the effects was minimised by the large spatial variability within the plots. Despite these shortcomings, simulated concentrations were generally within the 95% confidence interval of the measurements although the effect of a reduction in N deposition on soil solution chemistry was underestimated due to a marked decline in N-uptake by the vegetation.

The New Color of Chemistry: Green Chemistry

Directory of Open Access Journals (Sweden)

Zuhal GERÇEK

2012-01-01

Full Text Available Green chemistry which is the new application of chemistry rules provides solutions to problems that mankind is faced with climate changes, sustainable agriculture, energy, toxics, depletion of natural sources e.g. designing new chemicals and processes that production and utilization of hazardous matters. So, it is the indispensible tool for sustainable development. Current and future chemists should consider the human health and ecological issues in their professional life. In order to provide a solution for this requirement, green chemistry rules and under standings should be primarily taken in the university curriculum and at all educational levels.

Simplified Model for Reburning Chemistry

DEFF Research Database (Denmark)

Glarborg, Peter; Hansen, Stine

2010-01-01

In solid fuel flames, reburn-type reactions are often important for the concentrations of NOx in the near-burner region. To be able to model the nitrogen chemistry in these flames, it is necessary to have an adequate model for volatile/NO interactions. Simple models consisting of global steps...

Complex chemistry

International Nuclear Information System (INIS)

Kim, Bong Gon; Kim, Jae Sang; Kim, Jin Eun; Lee, Boo Yeon

2006-06-01

This book introduces complex chemistry with ten chapters, which include development of complex chemistry on history coordination theory and Warner's coordination theory and new development of complex chemistry, nomenclature on complex with conception and define, chemical formula on coordination compound, symbol of stereochemistry, stereo structure and isomerism, electron structure and bond theory on complex, structure of complex like NMR and XAFS, balance and reaction on solution, an organo-metallic chemistry, biology inorganic chemistry, material chemistry of complex, design of complex and calculation chemistry.

Chemistry models in the Victoria code

International Nuclear Information System (INIS)

Grimley, A.J. III

1988-01-01

The VICTORIA Computer code consists of the fission product release and chemistry models for the MELPROG severe accident analysis code. The chemistry models in VICTORIA are used to treat multi-phase interactions in four separate physical regions: fuel grains, gap/open porosity/clad, coolant/aerosols, and structure surfaces. The physical and chemical environment of each region is very different from the others and different models are required for each. The common thread in the modelling is the use of a chemical equilibrium assumption. The validity of this assumption along with a description of the various physical constraints applicable to each region will be discussed. The models that result from the assumptions and constraints will be presented along with samples of calculations in each region

A time-dependent anisotropic plasma chemistry model of the Io plasma torus

Science.gov (United States)

Arridge, C. S.

2016-12-01

The physics of the Io plasma torus is typically modelled using one box neutral-plasma chemistry models, often referred to as neutral cloud theory models (e.g., Barbosa 1994; Delamere and Bagenal 2003). These models incorporate electron impact and photoionisation, charge exchange, molecular dissociation/recombination reactions, atomic radiatiative losses and Coulomb collisional heating. Isotropic Maxwellian distributions are usually assumed in the implementation of these models. Observationally a population of suprathermal electrons has been identified in the plasma torus and theoretically they have been shown to be important in reproducing the observed ionisation balance in the torus (e.g., Barbosa 1994). In this paper we describe an anisotropic plasma chemistry model for the Io torus that is inspired by ion cyclotron wave observations (Huddleston et al. 1994; Leisner et al. 2011), ion anisotropies due to pick up (Wilson et al. 2008), and theoretical ideas on the maintenance of the suprathermal electron population (Barbosa 1994). We present both steady state calculations and also time varying solutions (e.g., Delamere et al. 2004) where increases in the neutral source rate in the torus generates perturbations in ion anisotropies that subsequently decay over a timescale much longer than the duration of the initial perturbation. We also present a method for incorporating uncertainties in reaction rates into the model.

Modeling local chemistry in PWR steam generator crevices

International Nuclear Information System (INIS)

Millett, P.J.

1997-01-01

Over the past two decades steam generator corrosion damage has been a major cost impact to PWR owners. Crevices and occluded regions create thermal-hydraulic conditions where aggressive impurities can become highly concentrated, promoting localized corrosion of the tubing and support structure materials. The type of corrosion varies depending on the local conditions, with stress corrosion cracking being the phenomenon of most current concern. A major goal of the EPRI research in this area has been to develop models of the concentration process and resulting crevice chemistry conditions. These models may then be used to predict crevice chemistry based on knowledge of bulk chemistry, thereby allowing the operator to control corrosion damage. Rigorous deterministic models have not yet been developed; however, empirical approaches have shown promise and are reflected in current versions of the industry-developed secondary water chemistry guidelines

Molecular Structure of Salt Solutions: A New View of the Interface with Implications for Heterogeneous Atmospheric Chemistry

Czech Academy of Sciences Publication Activity Database

Jungwirth, Pavel; Tobias, D. J.

2001-01-01

Roč. 105, č. 43 (2001), s. 10468-10472 ISSN 1089-5647 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : air-solution interface * salt solutions * molecular dynamics Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.379, year: 2001

The 1-way on-line coupled atmospheric chemistry model system MECO(n – Part 1: Description of the limited-area atmospheric chemistry model COSMO/MESSy

Directory of Open Access Journals (Sweden)

A. Kerkweg

2012-01-01

Full Text Available The numerical weather prediction model of the Consortium for Small Scale Modelling (COSMO, maintained by the German weather service (DWD, is connected with the Modular Earth Submodel System (MESSy. This effort is undertaken in preparation of a new, limited-area atmospheric chemistry model. Limited-area models require lateral boundary conditions for all prognostic variables. Therefore the quality of a regional chemistry model is expected to improve, if boundary conditions for the chemical constituents are provided by the driving model in consistence with the meteorological boundary conditions. The new developed model is as consistent as possible, with respect to atmospheric chemistry and related processes, with a previously developed global atmospheric chemistry general circulation model: the ECHAM/MESSy Atmospheric Chemistry (EMAC model. The combined system constitutes a new research tool, bridging the global to the meso-γ scale for atmospheric chemistry research. MESSy provides the infrastructure and includes, among others, the process and diagnostic submodels for atmospheric chemistry simulations. Furthermore, MESSy is highly flexible allowing model setups with tailor made complexity, depending on the scientific question. Here, the connection of the MESSy infrastructure to the COSMO model is documented and also the code changes required for the generalisation of regular MESSy submodels. Moreover, previously published prototype submodels for simplified tracer studies are generalised to be plugged-in and used in the global and the limited-area model. They are used to evaluate the TRACER interface implementation in the new COSMO/MESSy model system and the tracer transport characteristics, an important prerequisite for future atmospheric chemistry applications. A supplementary document with further details on the technical implementation of the MESSy interface into COSMO with a complete list of modifications to the COSMO code is provided.

Application of a coupled ecosystem-chemical equilibrium model, DayCent-Chem, to stream and soil chemistry in a Rocky Mountain watershed

Science.gov (United States)

Hartman, M.D.; Baron, Jill S.; Ojima, D.S.

2007-01-01

Atmospheric deposition of sulfur and nitrogen species have the potential to acidify terrestrial and aquatic ecosystems, but nitrate and ammonium are also critical nutrients for plant and microbial productivity. Both the ecological response and the hydrochemical response to atmospheric deposition are of interest to regulatory and land management agencies. We developed a non-spatial biogeochemical model to simulate soil and surface water chemistry by linking the daily version of the CENTURY ecosystem model (DayCent) with a low temperature aqueous geochemical model, PHREEQC. The coupled model, DayCent-Chem, simulates the daily dynamics of plant production, soil organic matter, cation exchange, mineral weathering, elution, stream discharge, and solute concentrations in soil water and stream flow. By aerially weighting the contributions of separate bedrock/talus and tundra simulations, the model was able to replicate the measured seasonal and annual stream chemistry for most solutes for Andrews Creek in Loch Vale watershed, Rocky Mountain National Park. Simulated soil chemistry, net primary production, live biomass, and soil organic matter for forest and tundra matched well with measurements. This model is appropriate for accurately describing ecosystem and surface water chemical response to atmospheric deposition and climate change. ?? 2006 Elsevier B.V. All rights reserved.

Uncertainty estimation and ensemble forecast with a chemistry-transport model - Application to air-quality modeling and simulation

International Nuclear Information System (INIS)

Mallet, Vivien

2005-01-01

The thesis deals with the evaluation of a chemistry-transport model, not primarily with classical comparisons to observations, but through the estimation of its a priori uncertainties due to input data, model formulation and numerical approximations. These three uncertainty sources are studied respectively on the basis of Monte Carlos simulations, multi-models simulations and numerical schemes inter-comparisons. A high uncertainty is found, in output ozone concentrations. In order to overtake the limitations due to the uncertainty, a solution is ensemble forecast. Through combinations of several models (up to forty-eight models) on the basis of past observations, the forecast can be significantly improved. The achievement of this work has also led to develop the innovative modelling-system Polyphemus. (author) [fr

Comparison of Chain Conformation of Poly(vinyl alcohol) in Solutions and Melts from Quantum Chemistry Based Molecular Dynamics Simulations

Science.gov (United States)

Jaffe, Richard; Han, Jie; Matsuda, Tsunetoshi; Yoon, Do; Langhoff, Stephen R. (Technical Monitor)

1997-01-01

Confirmations of 2,4-dihydroxypentane (DHP), a model molecule for poly(vinyl alcohol), have been studied by quantum chemistry (QC) calculations and molecular dynamics (MD) simulations. QC calculations at the 6-311G MP2 level show the meso tt conformer to be lowest in energy followed by the racemic tg, due to intramolecular hydrogen bond between the hydroxy groups. The Dreiding force field has been modified to reproduce the QC conformer energies for DHP. MD simulations using this force field have been carried out for DHP molecules in the gas phase, melt, and CHCl3 and water solutions. Extensive intramolecular hydrogen bonding is observed for the gas phase and CHCl3 solution, but not for the melt or aqueous solution, Such a condensed phase effect due to intermolecular interactions results in a drastic change in chain conformations, in agreement with experiments.

GEOS-5 Chemistry Transport Model User's Guide

Science.gov (United States)

Kouatchou, J.; Molod, A.; Nielsen, J. E.; Auer, B.; Putman, W.; Clune, T.

2015-01-01

The Goddard Earth Observing System version 5 (GEOS-5) General Circulation Model (GCM) makes use of the Earth System Modeling Framework (ESMF) to enable model configurations with many functions. One of the options of the GEOS-5 GCM is the GEOS-5 Chemistry Transport Model (GEOS-5 CTM), which is an offline simulation of chemistry and constituent transport driven by a specified meteorology and other model output fields. This document describes the basic components of the GEOS-5 CTM, and is a user's guide on to how to obtain and run simulations on the NCCS Discover platform. In addition, we provide information on how to change the model configuration input files to meet users' needs.

A four-dimensional variational chemistry data assimilation scheme for Eulerian chemistry transport modeling

Science.gov (United States)

Eibern, Hendrik; Schmidt, Hauke

1999-08-01

The inverse problem of data assimilation of tropospheric trace gas observations into an Eulerian chemistry transport model has been solved by the four-dimensional variational technique including chemical reactions, transport, and diffusion. The University of Cologne European Air Pollution Dispersion Chemistry Transport Model 2 with the Regional Acid Deposition Model 2 gas phase mechanism is taken as the basis for developing a full four-dimensional variational data assimilation package, on the basis of the adjoint model version, which includes the adjoint operators of horizontal and vertical advection, implicit vertical diffusion, and the adjoint gas phase mechanism. To assess the potential and limitations of the technique without degrading the impact of nonperfect meteorological analyses and statistically not established error covariance estimates, artificial meteorological data and observations are used. The results are presented on the basis of a suite of experiments, where reduced records of artificial "observations" are provided to the assimilation procedure, while other "data" is retained for performance control of the analysis. The paper demonstrates that the four-dimensional variational technique is applicable for a comprehensive chemistry transport model in terms of computational and storage requirements on advanced parallel platforms. It is further shown that observed species can generally be analyzed, even if the "measurements" have unbiased random errors. More challenging experiments are presented, aiming to tax the skill of the method (1) by restricting available observations mostly to surface ozone observations for a limited assimilation interval of 6 hours and (2) by starting with poorly chosen first guess values. In this first such application to a three-dimensional chemistry transport model, success was also achieved in analyzing not only observed but also chemically closely related unobserved constituents.

Analytical chemistry

Energy Technology Data Exchange (ETDEWEB)

Chae, Myeong Hu; Lee, Hu Jun; Kim, Ha Seok

1989-02-15

This book give explanations on analytical chemistry with ten chapters, which deal with development of analytical chemistry, the theory of error with definition and classification, sample and treatment gravimetry on general process of gravimetry in aqueous solution and non-aqueous solution, precipitation titration about precipitation reaction and types, complexometry with summary and complex compound, oxidation-reduction equilibrium on electrode potential and potentiometric titration, solvent extraction and chromatograph and experiment with basic operation for chemical experiment.

Analytical chemistry

International Nuclear Information System (INIS)

Chae, Myeong Hu; Lee, Hu Jun; Kim, Ha Seok

1989-02-01

This book give explanations on analytical chemistry with ten chapters, which deal with development of analytical chemistry, the theory of error with definition and classification, sample and treatment gravimetry on general process of gravimetry in aqueous solution and non-aqueous solution, precipitation titration about precipitation reaction and types, complexometry with summary and complex compound, oxidation-reduction equilibrium on electrode potential and potentiometric titration, solvent extraction and chromatograph and experiment with basic operation for chemical experiment.

General chemistry

International Nuclear Information System (INIS)

Kwon, Yeong Sik; Lee, Dong Seop; Ryu, Haung Ryong; Jang, Cheol Hyeon; Choi, Bong Jong; Choi, Sang Won

1993-07-01

The book concentrates on the latest general chemistry, which is divided int twenty-three chapters. It deals with basic conception and stoichiometry, nature of gas, structure of atoms, quantum mechanics, symbol and structure of an electron of ion and molecule, chemical thermodynamics, nature of solid, change of state and liquid, properties of solution, chemical equilibrium, solution and acid-base, equilibrium of aqueous solution, electrochemistry, chemical reaction speed, molecule spectroscopy, hydrogen, oxygen and water, metallic atom; 1A, IIA, IIIA, carbon and atom IVA, nonmetal atom and an inert gas, transition metals, lanthanons, and actinoids, nuclear properties and radioactivity, biochemistry and environment chemistry.

Effect of solution chemistry on the adsorption of perfluorooctane sulfonate onto mineral surfaces.

Science.gov (United States)

Tang, Chuyang Y; Shiang Fu, Q; Gao, Dawen; Criddle, Craig S; Leckie, James O

2010-04-01

Perfluorooctane sulfonate (PFOS) is an emergent contaminant of substantial environmental concerns, yet very limited information has been available on PFOS adsorption onto mineral surfaces. PFOS adsorption onto goethite and silica was investigated by batch adsorption experiments under various solution compositions. Adsorption onto silica was only marginally affected by pH, ionic strength, and calcium concentration, likely due to the dominance of non-electrostatic interactions. In contrast, PFOS uptake by goethite increased significantly at high [H+] and [Ca2+], which was likely due to enhanced electrostatic attraction between the negatively charged PFOS molecules and positively charged goethite surface. The effect of pH was less significant at high ionic strength, likely due to electrical double layer compression. PFOS uptake was reduced at higher ionic strength for a strongly positively charged goethite surface (pH 3), while it increased for a weakly charged surface (pH 7 and 9), which could be attributed to the competition between PFOS-surface electrostatic attraction and PFOS-PFOS electrostatic repulsion. A conceptual model that captures PFOS-surface and PFOS-PFOS electrostatic interactions as well as non-electrostatic interaction was also formulated to understand the effect of solution chemistry on PFOS adsorption onto goethite and silica surfaces. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Theoretical chemistry advances and perspectives

CERN Document Server

Eyring, Henry

1980-01-01

Theoretical Chemistry: Advances and Perspectives, Volume 5 covers articles concerning all aspects of theoretical chemistry. The book discusses the mean spherical approximation for simple electrolyte solutions; the representation of lattice sums as Mellin-transformed products of theta functions; and the evaluation of two-dimensional lattice sums by number theoretic means. The text also describes an application of contour integration; a lattice model of quantum fluid; as well as the computational aspects of chemical equilibrium in complex systems. Chemists and physicists will find the book usef

High fidelity chemistry and radiation modeling for oxy -- combustion scenarios

Science.gov (United States)

Abdul Sater, Hassan A.

To account for the thermal and chemical effects associated with the high CO2 concentrations in an oxy-combustion atmosphere, several refined gas-phase chemistry and radiative property models have been formulated for laminar to highly turbulent systems. This thesis examines the accuracies of several chemistry and radiative property models employed in computational fluid dynamic (CFD) simulations of laminar to transitional oxy-methane diffusion flames by comparing their predictions against experimental data. Literature review about chemistry and radiation modeling in oxy-combustion atmospheres considered turbulent systems where the predictions are impacted by the interplay and accuracies of the turbulence, radiation and chemistry models. Thus, by considering a laminar system we minimize the impact of turbulence and the uncertainties associated with turbulence models. In the first section of this thesis, an assessment and validation of gray and non-gray formulations of a recently proposed weighted-sum-of-gray gas model in oxy-combustion scenarios was undertaken. Predictions of gas, wall temperatures and flame lengths were in good agreement with experimental measurements. The temperature and flame length predictions were not sensitive to the radiative property model employed. However, there were significant variations between the gray and non-gray model radiant fraction predictions with the variations in general increasing with decrease in Reynolds numbers possibly attributed to shorter flames and steeper temperature gradients. The results of this section confirm that non-gray model predictions of radiative heat fluxes are more accurate than gray model predictions especially at steeper temperature gradients. In the second section, the accuracies of three gas-phase chemistry models were assessed by comparing their predictions against experimental measurements of temperature, species concentrations and flame lengths. The chemistry was modeled employing the Eddy

The link between physics and chemistry in track modelling

International Nuclear Information System (INIS)

Green, N.J.B.; Bolton, C.E.; Spencer-Smith, R.D.

1999-01-01

The physical structure of a radiation track provides the initial conditions for the modelling of radiation chemistry. These initial conditions are not perfectly understood, because there are important gaps between what is provided by a typical track structure model and what is required to start the chemical model. This paper addresses the links between the physics and chemistry of tracks, with the intention of identifying those problems that need to be solved in order to obtain an accurate picture of the initial conditions for the purposes of modelling chemistry. These problems include the reasons for the increased yield of ionisation relative to homolytic bond breaking in comparison with the gas phase. A second area of great importance is the physical behaviour of low-energy electrons in condensed matter (including thermolisation and solvation). Many of these processes are not well understood, but they can have profound effects on the transient chemistry in the track. Several phenomena are discussed, including the short distance between adjacent energy loss events, the molecular nature of the underlying medium, dissociative attachment resonances and the ability of low-energy electrons to excite optically forbidden molecular states. Each of these phenomena has the potential to modify the transient chemistry substantially and must therefore be properly characterised before the physical model of the track can be considered to be complete. (orig.)

Solute-specific patterns and drivers of urban stream chemistry revealed by long-term monitoring in Baltimore, Maryland

Science.gov (United States)

Reisinger, A. J.; Woytowitz, E.; Majcher, E.; Rosi, E. J.; Groffman, P.

2017-12-01

Urban streams receive a myriad of chemical inputs from the surrounding landscape due to altered lithology (asphalt, concrete), leaky sewage infrastructure, and other human activities (road salt, fertilizer, industrial wastes, wastewater effluent), potentially leading to multiple chemical stressors occurring simultaneously. To evaluate potential drivers of water chemistry change, we used approximately 20 years of weekly water chemistry monitoring data from streams in the Baltimore Ecosystem Study (BES) to quantify trends of annual loads and flow-weighted concentrations for multiple solutes of interest, including nitrate (NO3-), phosphate (PO43-), total nitrogen (TN), total phosphorus (TP), chloride (Cl-), and sulfate (SO42-) and subsequently examined various gray and green infrastructure characteristics at the watershed scale. For example, we quantified annual volume and duration of reported sanitary sewer overflows (SSO) and cumulative storage volume and area of various best management practices (BMPs). Site- and solute-specific trends differed, but across our monitoring network we found evidence for decreasing annual export for multiple solutes. Additionally, we found that changes in gray- and green-infrastructure characteristics were related to changes in water quality at our most downstream (most urban) monitoring site. For example, annual NO3- loads increased with longer cumulative SSO duration, whereas annual PO43- and TP loads decreased with a cumulative BMP area in the watershed. Further, we used same long-term water chemistry data and multivariate analyses to investigate whether urban streams have unique water chemistry fingerprints representing the multiple chemical stressors at a given site, which could provide insight into sources and impacts of water-quality impairment. These analyses and results illustrate the major role gray and green infrastructure play in influencing water quality in urban environments, and illustrate that focusing on a variety of

XI International conference Problems of solvation and complex formation in solutions, and VI Conference of young scientists Theoretical and experimental chemistry of liquid-phase systems (Krestovsky readings). Summary of reports

International Nuclear Information System (INIS)

2011-01-01

The collection contains materials of plenary, sectional and poster sessions, presented at the XI International conference Problems of solvation and complex formation in solutions, and VI Conference of young scientists Theoretical and experimental chemistry of liquid-phase systems (Krestovsky readings). Theoretical questions and new experimental methods of chemistry of solutions, structure and dynamics of molecular and ion-molecular systems in solution and at the phase boundary; modern aspects of applied chemistry of solutions are discussed [ru

Modeling UTLS water vapor: Transport/Chemistry interactions

International Nuclear Information System (INIS)

Gulstad, Line

2005-01-01

This thesis was initially meant to be a study on the impact on chemistry and climate from UTLS water vapor. However, the complexity of the UTLS water vapor and its recent changes turned out to be a challenge by it self. In the light of this, the overall motivation for the thesis became to study the processes controlling UTLS water vapor and its changes. Water vapor is the most important greenhouse gas, involved in important climate feedback loops. Thus, a good understanding of the chemical and dynamical behavior of water vapor in the atmosphere is crucial for understanding the climate changes in the last century. Additionally, parts of the work was motivated by the development of a coupled climate chemistry model based on the CAM3 model coupled with the Chemical Transport Model Oslo CTM2. The future work will be concentrated on the UTLS water vapor impact on chemistry and climate. We are currently studying long term trends in UTLS water vapor, focusing on identification of the different processes involved in the determination of such trends. The study is based on natural as well as anthropogenic climate forcings. The ongoing work on the development of a coupled climate chemistry model will continue within our group, in collaboration with Prof. Wei-Chyung Wang at the State University of New York, Albany. Valuable contacts with observational groups are established during the work on this thesis. These collaborations will be continued focusing on continuous model validation, as well as identification of trends and new features in UTLS water vapor, and other tracers in this region. (Author)

Simulating the long-term chemistry of an upland UK catchment: Major solutes and acidification

Energy Technology Data Exchange (ETDEWEB)

Tipping, E. [Centre for Ecology and Hydrology (Lancaster), Library Avenue, Bailrigg, Lancaster LA1 4AP (United Kingdom)]. E-mail: et@ceh.ac.uk; Lawlor, A.J. [Centre for Ecology and Hydrology (Lancaster), Library Avenue, Bailrigg, Lancaster LA1 4AP (United Kingdom); Lofts, S. [Centre for Ecology and Hydrology (Lancaster), Library Avenue, Bailrigg, Lancaster LA1 4AP (United Kingdom)

2006-05-15

CHUM-AM was used to investigate changes in soil and water chemical variables in four moorland sub-catchments in Cumbria UK, to which non-marine S deposition has declined by 65% since the 1970s. The principal processes represented in the model comprise N and S uptake and release, water movements, the binding of cations by soil organic matter, chemical interactions in solution, and chemical weathering. CHUM-AM reproduced reasonably well the current soil pH and pools of N and S, and changes in streamwater chemistry over the period 1970-2000, notably decreases in the concentrations of alkaline earth cations and sulphate, and increases in pH. The model also predicts streamwater pH-Al relationships in agreement with observations. Predictive calculations suggest that constant atmospheric deposition of N at present rates will lead to N saturation and re-acidification, whereas a 50% reduction in N would stabilise soil and streamwater pH at about the present levels. - CHUM-AM accounts for recovery from acidification due to sulphur deposition, but predicts re-acidification if nitrogen deposition is not reduced.

Solution chemistry of carbonate minerals and its effects on the flotation of hematite with sodium oleate

Science.gov (United States)

Li, Dong; Yin, Wan-zhong; Xue, Ji-wei; Yao, Jin; Fu, Ya-feng; Liu, Qi

2017-07-01

The effects of carbonate minerals (dolomite and siderite) on the flotation of hematite using sodium oleate as a collector were investigated through flotation tests, supplemented by dissolution measurements, solution chemistry calculations, zeta-potential measurements, Fourier transform infrared (FTIR) spectroscopic studies, and X-ray photoelectron spectroscopy (XPS) analyses. The results of flotation tests show that the presence of siderite or dolomite reduced the recovery of hematite and that the inhibiting effects of dolomite were stronger. Dissolution measurements, solution chemistry calculations, and flotation tests confirmed that both the cations (Ca2+ and Mg2+) and CO3 2- ions dissolved from dolomite depressed hematite flotation, whereas only the CO3 2- ions dissolved from siderite were responsible for hematite depression. The zeta-potential, FTIR spectroscopic, and XPS analyses indicated that Ca2+, Mg2+, and CO3 2- (HCO3 -) could adsorb onto the hematite surface, thereby hindering the adsorption of sodium oleate, which was the main reason for the inhibiting effects of carbonate minerals on hematite flotation.

Radiation chemistry

International Nuclear Information System (INIS)

Swallow, A.J.

1983-01-01

The subject is covered in chapters, entitled: introduction (defines scope of article as dealing with the chemistry of reactive species, (e.g. excess electrons, excited states, free radicals and inorganic ions in unusual valency states) as studied using radiation with radiation chemistry in its traditional sense and with biological and industrial applications); gases; water and simple inorganic systems; aqueous metallo-organic compounds and metalloproteins; small organic molecules in aqueous solution; microheterogeneous systems; non-aqueous liquids and solutions; solids; biological macromolecules; synthetic polymers. (U.K.)

Chemistry education based on concepts represented by mental models

OpenAIRE

Gibin, Gustavo Bizarria; Ferreira, Luiz Henrique

2010-01-01

The current legislation determines that the chemist must have a solid comprehension about chemical concepts. Literature presents the concept of mental model, which is determinant to the learning of phenomena and concepts. This paper presents some mental models that students of the Chemistry course at UFSCar have about chemical concepts. A lot of incoherence was observed in student's mental models, which is an evidence that there are problems in the learning of chemistry education.

Parameterization and evaluation of sulfate adsorption in a dynamic soil chemistry model

International Nuclear Information System (INIS)

Martinson, Liisa; Alveteg, Mattias; Warfvinge, Per

2003-01-01

Including sulfate adsorption improves the dynamic behavior of the SAFE model. - Sulfate adsorption was implemented in the dynamic, multi-layer soil chemistry model SAFE. The process is modeled by an isotherm in which sulfate adsorption is considered to be fully reversible and dependent on sulfate concentration as well as pH in soil solution. The isotherm was parameterized by a site-specific series of simple batch experiments at different pH (3.8-5.0) and sulfate concentration (10-260 μmol l -1 ) levels. Application of the model to the Lake Gaardsjoen roof covered site shows that including sulfate adsorption improves the dynamic behavior of the model and sulfate adsorption and desorption delay acidification and recovery of the soil. The modeled adsorbed pool of sulfate at the site reached a maximum level of 700 mmol/m 2 in the late 1980s, well in line with experimental data

Porewater chemistry in compacted bentonite

Energy Technology Data Exchange (ETDEWEB)

Muurinen, A.; Lehikoinen, J. [VTT Chemical Technology, Espoo (Finland)

1999-03-01

In this study, the porewater chemistry in compacted bentonite, considered as an engineered barrier in the repository of spent fuel, has been studied in interaction experiments. Many parameters, like the composition and density of bentonite, composition of the solution, bentonite-to-water ratio (B/W), surrounding conditions and experimental time have been varied in the experiments. At the end of the interaction the equilibrating solution, the porewaters squeezed out of the bentonite samples, and bentonites themselves were analyzed to give information for the interpretation and modelling of the interaction. Equilibrium modelling was performed with the HYDRAQL/CE computer code 33 refs.

Use of chemistry software to teach and assess model-based reaction and equation knowledge

Directory of Open Access Journals (Sweden)

Kevin Pyatt

2014-12-01

Full Text Available This study investigated the challenges students face when learning chemical reactions in a first-year chemistry course and the effectiveness of a curriculum and software implementation that was used to teach and assess student understanding of chemical reactions and equations. This study took place over a two year period in a public suburban high-school, in southwestern USA. Two advanced placement (AP chemistry classes participated, referred to here as study group A (year 1, N = 14; and study group B (year 2, N = 21. The curriculum for a first-year chemistry course (group A was revised to include instruction on reaction-types. The second year of the study involved the creation and implementation of a software solution which promoted mastery learning of reaction-types. Students in both groups benefited from the reaction-type curriculum and achieved proficiency in chemical reactions and equations.  The findings suggest there was an added learning benefit to using the reaction-type software solution. This study also found that reaction knowledge was a moderate to strong predictor of chemistry achievement. Based on regression analysis, reaction knowledge significantly predicted chemistry achievement for both groups.

One-Dimensional Transport with Equilibrium Chemistry (OTEQ) - A Reactive Transport Model for Streams and Rivers

Science.gov (United States)

Runkel, Robert L.

2010-01-01

OTEQ is a mathematical simulation model used to characterize the fate and transport of waterborne solutes in streams and rivers. The model is formed by coupling a solute transport model with a chemical equilibrium submodel. The solute transport model is based on OTIS, a model that considers the physical processes of advection, dispersion, lateral inflow, and transient storage. The equilibrium submodel is based on MINTEQ, a model that considers the speciation and complexation of aqueous species, acid-base reactions, precipitation/dissolution, and sorption. Within OTEQ, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (waterborne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach. The model's ability to simulate pH, precipitation/dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between instream chemistry and hydrologic transport at the field scale. This report details the development and application of OTEQ. Sections of the report describe model theory, input/output specifications, model applications, and installation instructions. OTEQ may be obtained over the Internet at http://water.usgs.gov/software/OTEQ.

The chemistry of high temperature phosphate solutions in relation to steam generation

International Nuclear Information System (INIS)

Broadbent, D.; Lewis, G.G.; Wetton, E.A.M.

1978-01-01

The problems associated with the use of phosphate for chemical treatment of the P.W.R. secondary circuit have prompted renewed interest in the physical chemistry of these solutions. Solubility and phase studies have been carried out at 250, 300 and 350 0 C with solutions having sodium to phosphate ratios from 1.0 to above 3.0. A solid phase of ratio about 2.8 exists in equilibrium with a wide range of saturated solution compositions at each temperature. Invariant points at which three phases are in equilibrium have been identified and at the two higher temperatures a region of liquid-liquid immiscibility occurs. Phase diagrams have been constructed for each temperature from which it is possible to predict the compositional changes occurring during the isothermal evaporation process. The corrosivity of these phosphate solutions to a range of steel alloys is being studied, the results reported in the present work, however, are confined to mild steel in the temperature and phosphate composition ranges of the phase studies. The corrosion of mild steel is generally considerably less than in sodium hydroxide solutions of equivalent concentration. The dependence of corrosion rate on sodium and phosphate concentrations in not readily explicable in terms of the solubility and phase studies and it is thought that the solubility of iron in the phosphate solutions is an important rate-determining factor since several complex compounds containing sodium, phosphorus and ferrous iron are present in the corrosion films. (author)

Models of gas-grain chemistry in interstellar cloud cores with a stochastic approach to surface chemistry

Science.gov (United States)

Stantcheva, T.; Herbst, E.

2004-08-01

We present a gas-grain model of homogeneous cold cloud cores with time-independent physical conditions. In the model, the gas-phase chemistry is treated via rate equations while the diffusive granular chemistry is treated stochastically. The two phases are coupled through accretion and evaporation. A small network of surface reactions accounts for the surface production of the stable molecules water, formaldehyde, methanol, carbon dioxide, ammonia, and methane. The calculations are run for a time of 107 years at three different temperatures: 10 K, 15 K, and 20 K. The results are compared with those produced in a totally deterministic gas-grain model that utilizes the rate equation method for both the gas-phase and surface chemistry. The results of the different models are in agreement for the abundances of the gaseous species except for later times when the surface chemistry begins to affect the gas. The agreement for the surface species, however, is somewhat mixed. The average abundances of highly reactive surface species can be orders of magnitude larger in the stochastic-deterministic model than in the purely deterministic one. For non-reactive species, the results of the models can disagree strongly at early times, but agree to well within an order of magnitude at later times for most molecules. Strong exceptions occur for CO and H2CO at 10 K, and for CO2 at 20 K. The agreement seems to be best at a temperature of 15 K. As opposed to the use of the normal rate equation method of surface chemistry, the modified rate method is in significantly better agreement with the stochastic-deterministic approach. Comparison with observations of molecular ices in dense clouds shows mixed agreement.

Soil solution chemistry and element fluxes in three European heathlands and their responses to warming and drought

DEFF Research Database (Denmark)

Schmidt, I.K.; Tietema, A.; Williams, D.

2004-01-01

Soil water chemistry and element budgets were studied at three northwestern European Calluna vulgaris heathland sites in Denmark (DK), The Netherlands (NL), and Wales (UK). Responses to experimental nighttime warming and early summer drought were followed during a two-year period. Soil solution...

Chemistry Teachers' Knowledge and Application of Models

Science.gov (United States)

Wang, Zuhao; Chi, Shaohui; Hu, Kaiyan; Chen, Wenting

2014-01-01

Teachers' knowledge and application of model play an important role in students' development of modeling ability and scientific literacy. In this study, we investigated Chinese chemistry teachers' knowledge and application of models. Data were collected through test questionnaire and analyzed quantitatively and qualitatively. The result indicated…

The response of soil solution chemistry in European forests to decreasing acid deposition

DEFF Research Database (Denmark)

Johnson, James; Pannatier, Elisabeth Graf; Carnicelli, Stefano

2018-01-01

to emissions controls. In this study, we assessed the response of soil solution chemistry in mineral horizons of European forests to these changes. Trends in pH, acid neutralizing capacity (ANC), major ions, total aluminium (Altot) and dissolved organic carbon were determined for the period 1995–2012. Plots...... with at least 10 years of observations from the ICP Forests monitoring network were used. Trends were assessed for the upper mineral soil (10–20 cm, 104 plots) and subsoil (40–80 cm, 162 plots). There was a large decrease in the concentration of sulphate () in soil solution; over a 10‐year period (2000...... over the entire dataset. The response of soil solution acidity was nonuniform. At 10–20 cm, ANC increased in acid‐sensitive soils (base saturation ≤10%) indicating a recovery, but ANC decreased in soils with base saturation >10%. At 40–80 cm, ANC remained unchanged in acid‐sensitive soils (base...

ECHMERIT: A new on-line global mercury-chemistry model

Science.gov (United States)

Jung, G.; Hedgecock, I. M.; Pirrone, N.

2009-04-01

Mercury is a volatile metal, that is of concern because when deposited and transformed to methylmercury accumulates within the food-web. Due to the long lifetime of elemental mercury, which is the dominant fraction of mercury species in the atmosphere, mercury is prone to long-range transport and therefore distributed over the globe, transported and hence deposited even in regions far from anthropogenic emission sources. Mercury is released to the atmosphere from a variety of natural and anthropogenic sources, in elementary and oxidised forms, and as particulate mercury. It is then transported, but also transformed chemically in the gaseous phase, as well as in aqueous phase within cloud and rain droplets. Mercury (particularly its oxidised forms) is removed from the atmosphere though wet and dry deposition processes, a large fraction of deposited mercury is, after chemical or biological reduction, re-emitted to the atmosphere as elementary mercury. To investigate mercury chemistry and transport processes on the global scale, the new, global model ECHMERIT has been developed. ECHMERIT simulates meteorology, transport, deposition, photolysis and chemistry on-line. The general circulation model on which ECHMERIT is based is ECHAM5. Sophisticated chemical modules have been implemented, including gas phase chemistry based on the CBM-Z chemistry mechanism, as well as aqueous phase chemistry, both of which have been adapted to include Hg chemistry and Hg species gas-droplet mass transfer. ECHMERIT uses the fast-J photolysis routine. State-of-the-art procedures simulating wet and dry deposition and emissions were adapted and included in the model as well. An overview of the model structure, development, validation and sensitivity studies is presented.

Spectroscopy and chemistry of uranium IV

International Nuclear Information System (INIS)

Folcher, G.; Rigny, P.

1980-06-01

Different fundamental research papers on uranium IV are presented, some were never edited. Molecular spectroscopy was used for identification and structural study of uranium IV in aqueous or organic solutions. The fields studied are: coordination, stereochemistry, electronic structure and chemical properties. For interpretation of results some studies were made with solid compounds or with thorium compounds or thorium complexes. Knowledge of actinides chemistry is improved, uranium and thorium being models for 5 f ions, extractive chemistry is better understood and new applications are possible [fr

The extrapolar SWIFT-model: Fast stratospheric ozone chemistry for global climate models

OpenAIRE

Kreyling, Daniel

2016-01-01

The goal of this PhD-thesis was the development of a fast yet accurate chemistry scheme for an interactive calculation of the extrapolar stratospheric ozone layer. The SWIFT-model is mainly intended for use in Global Climate Models (GCMs). For computing-time reasons GCMs often do not employ full stratospheric chemistry modules, but use prescribed ozone instead. This method does not consider the interaction between atmospheric dynamics and the ozone layer and can neither resolve the inter-annu...

Application of modeling to local chemistry in PWR steam generators

International Nuclear Information System (INIS)

Fauchon, C.; Millett, P.J.; Ollar, P.

1998-01-01

Localized corrosion of the SG tubes and other components is due to the presence of an aggressive environment in local crevices and occluded regions. In crevices and on vertical and horizontal tube surfaces, corrosion products and particulate matter can accumulate in the form of porous deposits. The SG water contains impurities at extremely low levels (ppb). Low levels of non-volatile impurities, however, can be efficiently concentrated in crevices and sludge piles by a thermal hydraulic mechanism. The temperature gradient across the SG tube coupled with local flow starvation, produces local boiling in the sludge and crevices. Since mass transfer processes are inhibited in these geometries, the residual liquid becomes enriched in many of the species present in the SG water. The resulting concentrated solutions have been shown to be aggressive and can corrode the SG materials. This corrosion may occur under various conditions which result in different types of attack such as pitting, stress corrosion cracking, wastage and denting. A major goal of EPRI's research program has been the development of models of the concentration process and the resulting chemistry. An improved understanding should eventually allow utilities to reduce or eliminate the corrosion by the appropriate manipulation of the steam generator water chemistry and or crevice conditions. The application of these models to experimental data obtained for prototypical SG tube support crevices is described in this paper. The models adequately describe the key features of the experimental data allowing extrapolations to be made to plant conditions. (author)

Predictive Modeling in Actinide Chemistry and Catalysis

Energy Technology Data Exchange (ETDEWEB)

Yang, Ping [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2016-05-16

These are slides from a presentation on predictive modeling in actinide chemistry and catalysis. The following topics are covered in these slides: Structures, bonding, and reactivity (bonding can be quantified by optical probes and theory, and electronic structures and reaction mechanisms of actinide complexes); Magnetic resonance properties (transition metal catalysts with multi-nuclear centers, and NMR/EPR parameters); Moving to more complex systems (surface chemistry of nanomaterials, and interactions of ligands with nanoparticles); Path forward and conclusions.

Stratospheric General Circulation with Chemistry Model (SGCCM)

Science.gov (United States)

Rood, Richard B.; Douglass, Anne R.; Geller, Marvin A.; Kaye, Jack A.; Nielsen, J. Eric; Rosenfield, Joan E.; Stolarski, Richard S.

1990-01-01

In the past two years constituent transport and chemistry experiments have been performed using both simple single constituent models and more complex reservoir species models. Winds for these experiments have been taken from the data assimilation effort, Stratospheric Data Analysis System (STRATAN).

Evaluating the effects of variable water chemistry on bacterial transport during infiltration.

Science.gov (United States)

Zhang, Haibo; Nordin, Nahjan Amer; Olson, Mira S

2013-07-01

Bacterial infiltration through the subsurface has been studied experimentally under different conditions of interest and is dependent on a variety of physical, chemical and biological factors. However, most bacterial transport studies fail to adequately represent the complex processes occurring in natural systems. Bacteria are frequently detected in stormwater runoff, and may present risk of microbial contamination during stormwater recharge into groundwater. Mixing of stormwater runoff with groundwater during infiltration results in changes in local solution chemistry, which may lead to changes in both bacterial and collector surface properties and subsequent bacterial attachment rates. This study focuses on quantifying changes in bacterial transport behavior under variable solution chemistry, and on comparing the influences of chemical variability and physical variability on bacterial attachment rates. Bacterial attachment rate at the soil-water interface was predicted analytically using a combined rate equation, which varies temporally and spatially with respect to changes in solution chemistry. Two-phase Monte Carlo analysis was conducted and an overall input-output correlation coefficient was calculated to quantitatively describe the importance of physiochemical variation on the estimates of attachment rate. Among physical variables, soil particle size has the highest correlation coefficient, followed by porosity of the soil media, bacterial size and flow velocity. Among chemical variables, ionic strength has the highest correlation coefficient. A semi-reactive microbial transport model was developed within HP1 (HYDRUS1D-PHREEQC) and applied to column transport experiments with constant and variable solution chemistries. Bacterial attachment rates varied from 9.10×10(-3)min(-1) to 3.71×10(-3)min(-1) due to mixing of synthetic stormwater (SSW) with artificial groundwater (AGW), while bacterial attachment remained constant at 9.10×10(-3)min(-1) in a constant

Teaching Chemistry with Electron Density Models

Science.gov (United States)

Shusterman, Gwendolyn P.; Shusterman, Alan J.

1997-07-01

Linus Pauling once said that a topic must satisfy two criteria before it can be taught to students. First, students must be able to assimilate the topic within a reasonable amount of time. Second, the topic must be relevant to the educational needs and interests of the students. Unfortunately, the standard general chemistry textbook presentation of "electronic structure theory", set as it is in the language of molecular orbitals, has a difficult time satisfying either criterion. Many of the quantum mechanical aspects of molecular orbitals are too difficult for most beginning students to appreciate, much less master, and the few applications that are presented in the typical textbook are too limited in scope to excite much student interest. This article describes a powerful new method for teaching students about electronic structure and its relevance to chemical phenomena. This method, which we have developed and used for several years in general chemistry (G.P.S.) and organic chemistry (A.J.S.) courses, relies on computer-generated three-dimensional models of electron density distributions, and largely satisfies Pauling's two criteria. Students find electron density models easy to understand and use, and because these models are easily applied to a broad range of topics, they successfully convey to students the importance of electronic structure. In addition, when students finally learn about orbital concepts they are better prepared because they already have a well-developed three-dimensional picture of electronic structure to fall back on. We note in this regard that the types of models we use have found widespread, rigorous application in chemical research (1, 2), so students who understand and use electron density models do not need to "unlearn" anything before progressing to more advanced theories.

Effects of simulated acid rain on soil and soil solution chemistry in a monsoon evergreen broad-leaved forest in southern China.

Science.gov (United States)

Qiu, Qingyan; Wu, Jianping; Liang, Guohua; Liu, Juxiu; Chu, Guowei; Zhou, Guoyi; Zhang, Deqiang

2015-05-01

Acid rain is an environmental problem of increasing concern in China. In this study, a laboratory leaching column experiment with acid forest soil was set up to investigate the responses of soil and soil solution chemistry to simulated acid rain (SAR). Five pH levels of SAR were set: 2.5, 3.0, 3.5, 4.0, and 4.5 (as a control, CK). The results showed that soil acidification would occur when the pH of SAR was ≤3.5. The concentrations of NO₃(-)and Ca(2+) in the soil increased significantly when the pH of SAR fell 3.5. The concentration of SO₄(2-) in the soil increased significantly when the pH of SAR was soil solution chemistry became increasingly apparent as the experiment proceeded (except for Na(+) and dissolved organic carbon (DOC)). The net exports of NO₃(-), SO₄(2-), Mg(2+), and Ca(2+) increased about 42-86% under pH 2.5 treatment as compared to CK. The Ca(2+) was sensitive to SAR, and the soil could release Ca(2+) through mineral weathering to mitigate soil acidification. The concentration of exchangeable Al(3+) in the soil increased with increasing the acidity of SAR. The releases of soluble Al and Fe were SAR pH dependent, and their net exports under pH 2.5 treatment were 19.6 and 5.5 times, respectively, higher than that under CK. The net export of DOC was reduced by 12-29% under SAR treatments as compared to CK. Our results indicate the chemical constituents in the soil are more sensitive to SAR than those in the soil solution, and the effects of SAR on soil solution chemistry depend not only on the intensity of SAR but also on the duration of SAR addition. The soil and soil solution chemistry in this region may not be affected by current precipitation (pH≈4.5) in short term, but the soil and soil leachate chemistry may change dramatically if the pH of precipitation were below 3.5 and 3.0, respectively.

Chemistry of americium

Energy Technology Data Exchange (ETDEWEB)

Schulz, W.W.

1976-01-01

Essential features of the descriptive chemistry of americium are reviewed. Chapter titles are: discovery, atomic and nuclear properties, collateral reading, production and uses, chemistry in aqueous solution, metal, alloys, and compounds, and, recovery, separation, purification. Author and subject indexes are included. (JCB)

The latest general chemistry

International Nuclear Information System (INIS)

Ryu, Geun Bae; Choi, Se Yeong; Kim, Chin Yeong; Yoon, Gil Jung; Lee, Eun Seok; Seo, Moon Gyu

1995-02-01

This book deals with the latest general chemistry, which is comprised of twenty-three chapters, the contents of this book are introduction, theory of atoms and molecule, chemical formula and a chemical reaction formula, structure of atoms, nature of atoms and the periodic table, structure of molecule and spectrum, gas, solution, solid, chemical combination, chemical reaction speed, chemical equilibrium, thermal chemistry, oxidation-reduction, electrochemistry, acid-base, complex, aquatic chemistry, air chemistry, nuclear chemistry, metal and nonmetal, organic chemistry and biochemistry. It has exercise in the end of each chapter.

SWIFT: Semi-empirical and numerically efficient stratospheric ozone chemistry for global climate models

OpenAIRE

Kreyling, Daniel; Wohltmann, Ingo; Lehmann, Ralph; Rex, Markus

2015-01-01

The SWIFT model is a fast yet accurate chemistry scheme for calculating the chemistry of stratospheric ozone. It is mainly intended for use in Global Climate Models (GCMs), Chemistry Climate Models (CCMs) and Earth System Models (ESMs). For computing time reasons these models often do not employ full stratospheric chem- istry modules, but use prescribed ozone instead. This can lead to insufficient representation between stratosphere and troposphere. The SWIFT stratospheric ozone chem...

The New Color of Chemistry: Green Chemistry

OpenAIRE

Zuhal GERÇEK

2012-01-01

Green chemistry which is the new application of chemistry rules provides solutions to problems that mankind is faced with climate changes, sustainable agriculture, energy, toxics, depletion of natural sources e.g. designing new chemicals and processes that production and utilization of hazardous matters. So, it is the indispensible tool for sustainable development. Current and future chemists should consider the human health and ecological issues in their professional life. In order to provid...

Reduction methods and uncertainty analysis: application to a Chemistry-Transport Model for modeling and simulation of impacts

International Nuclear Information System (INIS)

Boutahar, Jaouad

2004-01-01

In an integrated impact assessment, one has to test several scenarios of the model inputs or/and to identify the effects of model input uncertainties on the model outputs. In both cases, a large number of simulations of the model is necessary. That of course is not feasible with comprehensive Chemistry-Transport Model, due to the need for huge CPU times. Two approaches may be used in order to circumvent these difficulties: The first approach consists in reducing the computational cost of the original model by building a reduced model. Two reduction techniques are used: the first method, POD, is related to the statistical behaviour of the system and is based on a proper orthogonal decomposition of the solutions. The second method, is an efficient representation of the input/output behaviour through look-up tables. It describes the output model as an expansion of finite hierarchical correlated function in terms of the input variables. The second approach is based on reducing the number of models runs required by the standard Monte Carlo methods. It characterizes the probabilistic response of the uncertain model output as an expansion of orthogonal polynomials according to model inputs uncertainties. Then the classical Monte Carlo simulation can easily be used to compute the probability density of the uncertain output. Another key point in an integrated impact assessment is to develop strategies for the reduction of emissions by computing Source/Receptor matrices for several years of simulations. We proposed here an efficient method to calculate these matrices by using the adjoint model and in particular by defining the 'representative chemical day'. All of these methods are applied to POLAIR3D, a Chemistry-Transport model developed in this thesis. (author) [fr

Modelling electric discharge chemistry

International Nuclear Information System (INIS)

McFarlane, J.; Wren, J.C.

1991-07-01

The chemistry occurring in a electric discharge was modelled to predict how it would be influenced by discharge conditions. The discharge was characterized by a calculated Boltzmann electron-energy distribution, from which rate constants for electron-molecule processes in air were determined. These rate constants were used in a chemical kinetics calculation that also included reactions between neutral molecules, ions, free radicals and electronically excited species. The model describes how the discharge chemistry was influenced by humidity, electric field, electron number density, and concentrations of key reagents identified in the study. The use of an electric discharge to destroy airborne contaminant molecules was appraised, the targeted contaminants being CF 2 Cl 2 , HCN, and SO 2 . The modelling results indicate that an electric discharge should be able to remove HCN and CF 2 Cl 2 effectively, especially if the discharge conditions have been optimized. Effective destruction is achieved with a moderate electric field (over 1 x 10 -15 V.cm 2 ), a substantial electron number density (over 1 x 10 12 cm -3 ), and the presence of H 2 0 in the process air. The residence time in the discharge was also shown to be important in contaminant destruction. An attempt was made to explain the results of the electric discharge abatement of SO 2 , a component of a simulated flue-gas mixture. Results from the model indicate that the discharge parameters that increase the concentration of hydroxyl radical also increase the rate of decomposition of SO 2 . An objective of the study was to explain the apparent enhancement of SO 2 destruction by the presence of a small amount of NO 2 . It was thought that a likely explanation would be the stabilization of HOSO 2 , an important intermediate in the oxidation of SO 2 by NO 2 . (49 figs., 14 tabs., 75 refs.)

Multi-Scale Modelling of the Gamma Radiolysis of Nitrate Solutions

OpenAIRE

Horne, Gregory; Donoclift, Thomas; Sims, Howard E.; M. Orr, Robin; Pimblott, Simon

2016-01-01

A multi-scale modelling approach has been developed for the extended timescale long-term radiolysis of aqueous systems. The approach uses a combination of stochastic track structure and track chemistry as well as deterministic homogeneous chemistry techniques and involves four key stages; radiation track structure simulation, the subsequent physicochemical processes, nonhomogeneous diffusion-reaction kinetic evolution, and homogeneous bulk chemistry modelling. The first three components model...

Multiple solutions in the theory of direct current glow discharges: Effect of plasma chemistry and nonlocality, different plasma-producing gases, and 3D modelling

Energy Technology Data Exchange (ETDEWEB)

Almeida, P. G. C.; Benilov, M. S. [Departamento de Física, CCCEE, Universidade da Madeira, Largo do Município, 9000 Funchal (Portugal)

2013-10-15

The work is aimed at advancing the multiple steady-state solutions that have been found recently in the theory of direct current (DC) glow discharges. It is shown that an account of detailed plasma chemistry and non-locality of electron transport and kinetic coefficients results in an increase of the number of multiple solutions but does not change their pattern. Multiple solutions are shown to exist for discharges in argon and helium provided that discharge pressure is high enough. This result indicates that self-organization in DC glow microdischarges can be observed not only in xenon, which has been the case until recently, but also in other plasma-producing gases; a conclusion that has been confirmed by recent experiments. Existence of secondary bifurcations can explain why patterns of spots grouped in concentric rings, observed in the experiment, possess in many cases higher number of spots in outer rings than in inner ones.

Application of solution-mineral equilibrium chemistry to solution mining of uranium ores

International Nuclear Information System (INIS)

Riese, A.C.; Propp, C.J.

1980-01-01

Modern methods of uranium solution mining are typically accompanied by gains and losses of mass through reagent consumption by rock-forming minerals, with subsequent formation of clay minerals, gypsum, carbonates, and iron oxyhydroxides. A systematic approach to alleviate such problems involves the application of leach solutions that are in equilibrium with the host-rock minerals but in disequilibrium with the ore-forming minerals. This partial equilibrium can be approximated by solution-composition adjustments within the systems K 2 O-Al 2 O 3 SiO 2 -H 2 O and Na 2 O 3 -Al 2 O 3 SiO 2 -H 2 O. Uranium ore containing 0.15 percent U 3 O 8 from the Gulf Mineral Resources Corporation's Mariano Lake mine, the Smith Lake district of the Grants mineral belt, was collected for investigation. Presented are a theoretical evaluation of leachate data and an experimental treatment of the ore, which contained mainly K-feldspar, plagioclase feldspar, and quartz (with lesser amounts of micas, clay minerals, and organic carbonaceous material). Small-scale (less than or equal to 1 kg) column-leaching experiments were conducted to model the results of conventional leaching operations and to provide leachate solutions that could be compared with solutions calculated to be in equilibrium with the matrix minerals. Leach solutions employed include: 1) sulfuric acid, 2) sodium bicarbonate, and 3) sulfuric acid with 1.0 molal potassium chloride. The uranium concentrations in the sodium-bicarbonate leach solution and the acid-leach solution were about a gram per liter at the termination of the tests. However, the permeability of the ore in the acid leach was greatly reduced, owing to the formation of clay minerals. Uranium solubility in the leach column stabilized with the potassium-chloride solution was calculated from leachate compositions to be limited by the solubility of carnotite

Implementation of an Online Chemistry Model to a Large Eddy Simulation Model (PALM-4U0

Science.gov (United States)

Mauder, M.; Khan, B.; Forkel, R.; Banzhaf, S.; Russo, E. E.; Sühring, M.; Kanani-Sühring, F.; Raasch, S.; Ketelsen, K.

2017-12-01

Large Eddy Simulation (LES) models permit to resolve relevant scales of turbulent motion, so that these models can capture the inherent unsteadiness of atmospheric turbulence. However, LES models are so far hardly applied for urban air quality studies, in particular chemical transformation of pollutants. In this context, BMBF (Bundesministerium für Bildung und Forschung) funded a joint project, MOSAIK (Modellbasierte Stadtplanung und Anwendung im Klimawandel / Model-based city planning and application in climate change) with the main goal to develop a new highly efficient urban climate model (UCM) that also includes atmospheric chemical processes. The state-of-the-art LES model PALM; Maronga et al, 2015, Geosci. Model Dev., 8, doi:10.5194/gmd-8-2515-2015), has been used as a core model for the new UCM named as PALM-4U. For the gas phase chemistry, a fully coupled 'online' chemistry model has been implemented into PALM. The latest version of the Kinetic PreProcessor (KPP) Version 2.3, has been utilized for the numerical integration of chemical species. Due to the high computational demands of the LES model, compromises in the description of chemical processes are required. Therefore, a reduced chemistry mechanism, which includes only major pollutants namely O3, NO, NO2, CO, a highly simplified VOC chemistry and a small number of products have been implemented. This work shows preliminary results of the advection, and chemical transformation of atmospheric pollutants. Non-cyclic boundaries have been used for inflow and outflow in east-west directions while periodic boundary conditions have been implemented to the south-north lateral boundaries. For practical applications, our approach is to go beyond the simulation of single street canyons to chemical transformation, advection and deposition of air pollutants in the larger urban canopy. Tests of chemistry schemes and initial studies of chemistry-turbulence, transport and transformations are presented.

Computational modeling of chemical reactions and interstitial growth and remodeling involving charged solutes and solid-bound molecules.

Science.gov (United States)

Ateshian, Gerard A; Nims, Robert J; Maas, Steve; Weiss, Jeffrey A

2014-10-01

Mechanobiological processes are rooted in mechanics and chemistry, and such processes may be modeled in a framework that couples their governing equations starting from fundamental principles. In many biological applications, the reactants and products of chemical reactions may be electrically charged, and these charge effects may produce driving forces and constraints that significantly influence outcomes. In this study, a novel formulation and computational implementation are presented for modeling chemical reactions in biological tissues that involve charged solutes and solid-bound molecules within a deformable porous hydrated solid matrix, coupling mechanics with chemistry while accounting for electric charges. The deposition or removal of solid-bound molecules contributes to the growth and remodeling of the solid matrix; in particular, volumetric growth may be driven by Donnan osmotic swelling, resulting from charged molecular species fixed to the solid matrix. This formulation incorporates the state of strain as a state variable in the production rate of chemical reactions, explicitly tying chemistry with mechanics for the purpose of modeling mechanobiology. To achieve these objectives, this treatment identifies the specific theoretical and computational challenges faced in modeling complex systems of interacting neutral and charged constituents while accommodating any number of simultaneous reactions where reactants and products may be modeled explicitly or implicitly. Several finite element verification problems are shown to agree with closed-form analytical solutions. An illustrative tissue engineering analysis demonstrates tissue growth and swelling resulting from the deposition of chondroitin sulfate, a charged solid-bound molecular species. This implementation is released in the open-source program FEBio ( www.febio.org ). The availability of this framework may be particularly beneficial to optimizing tissue engineering culture systems by examining the

Modeling of iodine radiation chemistry in the presence of organic compounds

International Nuclear Information System (INIS)

Taghipour, Fariborz; Evans, Greg J.

2002-01-01

A kinetic-based model was developed that simulates the radiation chemistry of iodine in the presence of organic compounds. The model's mechanistic description of iodine chemistry and generic semi-mechanistic reactions for various classes of organics, provided a reasonable representation of experimental results. The majority of the model and experimental results of iodine volatilization rates were in agreement within an order of magnitude

MIANN models in medicinal, physical and organic chemistry.

Science.gov (United States)

González-Díaz, Humberto; Arrasate, Sonia; Sotomayor, Nuria; Lete, Esther; Munteanu, Cristian R; Pazos, Alejandro; Besada-Porto, Lina; Ruso, Juan M

2013-01-01

Reducing costs in terms of time, animal sacrifice, and material resources with computational methods has become a promising goal in Medicinal, Biological, Physical and Organic Chemistry. There are many computational techniques that can be used in this sense. In any case, almost all these methods focus on few fundamental aspects including: type (1) methods to quantify the molecular structure, type (2) methods to link the structure with the biological activity, and others. In particular, MARCH-INSIDE (MI), acronym for Markov Chain Invariants for Networks Simulation and Design, is a well-known method for QSAR analysis useful in step (1). In addition, the bio-inspired Artificial-Intelligence (AI) algorithms called Artificial Neural Networks (ANNs) are among the most powerful type (2) methods. We can combine MI with ANNs in order to seek QSAR models, a strategy which is called herein MIANN (MI & ANN models). One of the first applications of the MIANN strategy was in the development of new QSAR models for drug discovery. MIANN strategy has been expanded to the QSAR study of proteins, protein-drug interactions, and protein-protein interaction networks. In this paper, we review for the first time many interesting aspects of the MIANN strategy including theoretical basis, implementation in web servers, and examples of applications in Medicinal and Biological chemistry. We also report new applications of the MIANN strategy in Medicinal chemistry and the first examples in Physical and Organic Chemistry, as well. In so doing, we developed new MIANN models for several self-assembly physicochemical properties of surfactants and large reaction networks in organic synthesis. In some of the new examples we also present experimental results which were not published up to date.

Identification of Chemistry Learning Problems Viewed From Conceptual Change Model

OpenAIRE

Redhana, I. W; Sudria, I. B. N; Hidayat, I; Merta, L. M

2017-01-01

This study aimed at describing and explaining chemistry learning problems viewed from conceptual change model and misconceptions of students. The study was qualitative research of case study type conducted in one class of SMAN 1 Singaraja. Subjects of the study were a chemistry teacher and students. Data were obtained through classroom observation, interviews, and conception tests. The chemistry learning problems were grouped based on aspects of necessity, intelligibility, plausibility, and f...

The global change research center atmospheric chemistry model

Energy Technology Data Exchange (ETDEWEB)

Moraes, Jr., Francis Perry [Oregon Graduate Inst. of Science and Technology, Portland, OR (United States)

1995-01-01

This work outlines the development of a new model of the chemistry of the natural atmosphere. The model is 2.5-dimensional, having spatial coordinates height, latitude, and, the half-dimension, land and ocean. The model spans both the troposphere and stratosphere, although the troposphere is emphasized and the stratosphere is simple and incomplete. The chemistry in the model includes the O_x, HO_x, NO_x, and methane cycles in a highly modular fashion which allows model users great flexibility in selecting simulation parameters. A detailed modeled sensitivity analysis is also presented. A key aspect of the model is its inclusion of clouds. The model uses current understanding of the distribution and optical thickness of clouds to determine the true radiation distribution in the atmosphere. As a result, detailed studies of the radiative effects of clouds on the distribution of both oxidant concentrations and trace gas removal are possible. This work presents a beginning of this study with model results and discussion of cloud effects on the hydroxyl radical.

The complex synthesis and solid state chemistry of ceria-lanthana solid solutions prepared via a hexamethylenetetramine precipitation

International Nuclear Information System (INIS)

Fleming, P.G.; Holmes, J.D.; Otway, D.J.; Morris, M.A.

2011-01-01

Mixed oxide solid solutions are becoming ever more commercially important across a range of applications. However, their synthesis can be problematical. Here, we show that ceria-lanthana solid solutions can be readily prepared via simple precipitation using hexamethylenetetramine. However, the solution chemistry can be complex, which results in the precipitated particles having a complex structure and morphology. Great care must be taken in both the synthesis and characterisation to quantify the complexity of the product. Even very high heat treatments were not able to produce highly homogeneous materials and X-ray diffractions reveals the non-equilibrium form of particles prepared in this way. Unexpected crystal structures are revealed including a new metastable cubic La 2 O 3 phase. - Graphical abstract: The suggested mechanism for the formation of dual fluorite phase particles, where Step 1 corresponds to room temperature aging, Step 2; heating the solution to 90 deg. C, Step 3; cooling of the solution to room temperature, Step 4; calcination to 500 deg. C, Step 5; calcination to 700 deg. C and Step 6; calcination to 1300 deg. C. The terminology of e.g. La 1-x Ce x (OH) 3 is used to indicate the formation of a mixed oxy-hydroxy participate rather than a definitive assignment of stoichiometry. Similarly, La 1-y Ce y O 2 only implies a mixed solid solution. Highlights: → Mol% of prepared Ce-La oxides did not follow that of reactant mol%. → Complex reaction pathway found to be dependent on metal solution concentrations. → At certain concentrations core shell particles were found to form. → A reaction model was produced based on cationic solubility. → Report lanthana solubility higher than previously reported in CeO 2 .

Modeling emissions for three-dimensional atmospheric chemistry transport models.

Science.gov (United States)

Matthias, Volker; Arndt, Jan A; Aulinger, Armin; Bieser, Johannes; Denier Van Der Gon, Hugo; Kranenburg, Richard; Kuenen, Jeroen; Neumann, Daniel; Pouliot, George; Quante, Markus

2018-01-24

Poor air quality is still a threat for human health in many parts of the world. In order to assess measures for emission reductions and improved air quality, three-dimensional atmospheric chemistry transport modeling systems are used in numerous research institutions and public authorities. These models need accurate emission data in appropriate spatial and temporal resolution as input. This paper reviews the most widely used emission inventories on global and regional scale and looks into the methods used to make the inventory data model ready. Shortcomings of using standard temporal profiles for each emission sector are discussed and new methods to improve the spatio-temporal distribution of the emissions are presented. These methods are often neither top-down nor bottom-up approaches but can be seen as hybrid methods that use detailed information about the emission process to derive spatially varying temporal emission profiles. These profiles are subsequently used to distribute bulk emissions like national totals on appropriate grids. The wide area of natural emissions is also summarized and the calculation methods are described. Almost all types of natural emissions depend on meteorological information, which is why they are highly variable in time and space and frequently calculated within the chemistry transport models themselves. The paper closes with an outlook for new ways to improve model ready emission data, for example by using external databases about road traffic flow or satellite data to determine actual land use or leaf area. In a world where emission patterns change rapidly, it seems appropriate to use new types of statistical and observational data to create detailed emission data sets and keep emission inventories up-to-date. Emission data is probably the most important input for chemistry transport model (CTM) systems. It needs to be provided in high temporal and spatial resolution and on a grid that is in agreement with the CTM grid. Simple

Modeling the acid-base chemistry of organic solutes in Adirondack, New York, lakes

Science.gov (United States)

Driscoll, Charles T.; Lehtinen, Michael D.; Sullivan, Timothy J.

1994-02-01

Data from the large and diverse Adirondack Lake Survey were used to calibrate four simple organic acid analog models in an effort to quantify the influence of naturally occurring organic acids on lake water pH and acid-neutralizing capacity (ANC). The organic acid analog models were calibrated to observations of pH, dissolved organic carbon (DOC), and organic anion (An-) concentrations from a reduced data set representing 1128 individual lake samples, expressed as 41 observations of mean pH, in intervals of 0.1 pH units from pH 3.9 to 7.0. Of the four organic analog approaches examined, including the Oliver et al. (1983) model, as well as monoprotic, diprotic, and triprotic representations, the triprotic analog model yielded the best fit (r2 = 0.92) to the observed data. Moreover, the triprotic model was qualitatively consistent with observed patterns of change in organic solute charge density as a function of pH. A low calibrated value for the first H+ dissociation constant (pKal = 2.62) and the observation that organic anion concentrations were significant even at very low pH (acidic functional groups. Inclusion of organic acidity in model calculations resulted in good agreement between measured and predicted values of lake water pH and ANC. Assessments to project the response of surface waters to future changes in atmospheric deposition, through the use of acidification models, will need to include representations of organic acids in model structure to make accurate predictions of pH and ANC.

AECL research programs in chemistry

International Nuclear Information System (INIS)

Crocker, I.H.; Eastwood, T.A.; Smith, D.R.; Stewart, R.B.; Tomlinson, M.; Torgerson, D.F.

1980-09-01

Fundamental or underlying research in chemistry is being done in AECL laboratories to further the understanding of processes involved in current nuclear energy systems and maintain an awareness of progress at the frontiers of chemical research so that new advances can be turned to advantage in future AECL endeavours. The report introduces the current research topics and describes them briefly under the following headings: radiation chemistry, isotope separation, high temperature solution chemistry, fuel reprocessing chemistry, and analytical chemistry. (auth)

Transport of E. coli D21g with runoff water under different solution chemistry conditions and surface slopes

Science.gov (United States)

Tracer and indicator microbe runoff experiments were conducted to investigate the influence of solution chemistry on the transport, retention, and release of Escherichia coli D21g. Experiments were conducted in a chamber (2.25 m long, 0.15 m wide, and 0.16 m high) packed with ultrapure quartz sand (...

Modeling the Explicit Chemistry of Anthropogenic and Biogenic Organic Aerosols

Energy Technology Data Exchange (ETDEWEB)

Madronich, Sasha [Univ. Corporation for Atmospheric Research, Boulder, CO (United States)

2015-12-09

The atmospheric burden of Secondary Organic Aerosols (SOA) remains one of the most important yet uncertain aspects of the radiative forcing of climate. This grant focused on improving our quantitative understanding of SOA formation and evolution, by developing, applying, and improving a highly detailed model of atmospheric organic chemistry, the Generation of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) model. Eleven (11) publications have resulted from this grant.

Computational chemistry

Science.gov (United States)

Arnold, J. O.

1987-01-01

With the advent of supercomputers, modern computational chemistry algorithms and codes, a powerful tool was created to help fill NASA's continuing need for information on the properties of matter in hostile or unusual environments. Computational resources provided under the National Aerodynamics Simulator (NAS) program were a cornerstone for recent advancements in this field. Properties of gases, materials, and their interactions can be determined from solutions of the governing equations. In the case of gases, for example, radiative transition probabilites per particle, bond-dissociation energies, and rates of simple chemical reactions can be determined computationally as reliably as from experiment. The data are proving to be quite valuable in providing inputs to real-gas flow simulation codes used to compute aerothermodynamic loads on NASA's aeroassist orbital transfer vehicles and a host of problems related to the National Aerospace Plane Program. Although more approximate, similar solutions can be obtained for ensembles of atoms simulating small particles of materials with and without the presence of gases. Computational chemistry has application in studying catalysis, properties of polymers, all of interest to various NASA missions, including those previously mentioned. In addition to discussing these applications of computational chemistry within NASA, the governing equations and the need for supercomputers for their solution is outlined.

Green Chemistry

Energy Technology Data Exchange (ETDEWEB)

Collison, Melanie

2011-05-15

Green chemistry is the science of chemistry used in a way that will not use or create hazardous substances. Dr. Rui Resendes is working in this field at GreenCentre Canada, an offshoot of PARTEQ Innovations in Kingston, Ontario. GreenCentre's preliminary findings suggest their licensed product {sup S}witchable Solutions{sup ,} featuring 3 classes of solvents and a surfactant, may be useful in bitumen oil sands extraction.

Liquid flow along a solid surface reversibly alters interfacial chemistry.

Science.gov (United States)

Lis, Dan; Backus, Ellen H G; Hunger, Johannes; Parekh, Sapun H; Bonn, Mischa

2014-06-06

In nature, aqueous solutions often move collectively along solid surfaces (for example, raindrops falling on the ground and rivers flowing through riverbeds). However, the influence of such motion on water-surface interfacial chemistry is unclear. In this work, we combine surface-specific sum frequency generation spectroscopy and microfluidics to show that at immersed calcium fluoride and fused silica surfaces, flow leads to a reversible modification of the surface charge and subsequent realignment of the interfacial water molecules. Obtaining equivalent effects under static conditions requires a substantial change in bulk solution pH (up to 2 pH units), demonstrating the coupling between flow and chemistry. These marked flow-induced variations in interfacial chemistry should substantially affect our understanding and modeling of chemical processes at immersed surfaces. Copyright © 2014, American Association for the Advancement of Science.

Online-coupled meteorology and chemistry models: history, current status, and outlook

Directory of Open Access Journals (Sweden)

Y. Zhang

2008-06-01

Full Text Available The climate-chemistry-aerosol-cloud-radiation feedbacks are important processes occurring in the atmosphere. Accurately simulating those feedbacks requires fully-coupled meteorology, climate, and chemistry models and presents significant challenges in terms of both scientific understanding and computational demand. This paper reviews the history and current status of the development and application of online-coupled meteorology and chemistry models, with a focus on five representative models developed in the US including GATOR-GCMOM, WRF/Chem, CAM3, MIRAGE, and Caltech unified GCM. These models represent the current status and/or the state-of-the science treatments of online-coupled models worldwide. Their major model features, typical applications, and physical/chemical treatments are compared with a focus on model treatments of aerosol and cloud microphysics and aerosol-cloud interactions. Aerosol feedbacks to planetary boundary layer meteorology and aerosol indirect effects are illustrated with case studies for some of these models. Future research needs for model development, improvement, application, as well as major challenges for online-coupled models are discussed.

Guided-Inquiry Experiments for Physical Chemistry: The POGIL-PCL Model

Science.gov (United States)

Hunnicutt, Sally S.; Grushow, Alexander; Whitnell, Robert

2015-01-01

The POGIL-PCL project implements the principles of process-oriented, guided-inquiry learning (POGIL) in order to improve student learning in the physical chemistry laboratory (PCL) course. The inquiry-based physical chemistry experiments being developed emphasize modeling of chemical phenomena. In each experiment, students work through at least…

Chemistry of plutonium revealed

International Nuclear Information System (INIS)

Connick, R.E.

1992-01-01

In 1941 one goal of the Manhattan Project was to unravel the chemistry of the synthetic element plutonium as rapidly as possible. In this paper the work carried out at Berkeley from the spring of 1942 to the summer of 1945 is described briefly. The aqueous chemistry of plutonium is quite remarkable. Important insights were obtained from tracer experiments, but the full complexity was not revealed until macroscopic amounts (milligrams) became available. Because processes for separation from fission products were based on aqueous solutions, such solution chemistry was emphasized, particularly precipitation and oxidation-reduction behavior. The latter turned out to be unusually intricate when it was discovered that two more oxidation states existed in aqueous solution than had previously been suspected. Further, an equilibrium was rapidly established among the four aqueous oxidation states, while at the same time any three were not in equilibrium. These and other observations made while doing a crash study of a previously unknown element are reported

Water chemistry at RBMK plants: Problems and solutions

International Nuclear Information System (INIS)

Mamet, V.; Yurmanov, V.

2002-01-01

After around 15 years of operation RBMK-1000 units undergo a major refit, which includes safety system upgrading, fuel tube replacement, etc. The above upgrading has created problems for water chemistry. In particular, in late 80's in-core insertion time of the portion of control rods was reduced 10-fold thanks to a transfer from water to filming cooling of scram channels. Scram channels are cooled with inner surface water film cooling and nitrogen is injected into heads via special pipelines. Such cooling system modernization ensures fast insertion of absorber rods. The above upgrade intensified nitric acid radiolytic generation in water coolant and pH 25 value shift to acid conditions (up to 4.5). The results of corrosion tests in such conditions proved the necessity to improve water chemistry to ensure corrosion protection of scram/control rod and circuit components, especially those made out of aluminium alloy. Since 1990 the new revision of the RBMK-1000 water chemistry standard specified the new normal operational limit and action levels for possible temporary deviations of pH 25 value. RBMK plant specific measures were implemented at RBMK plants to meet the above requirements of the 1990 revision of the RBMK-1000 water chemistry standard. Clean-up systems of the above circuit were upgraded to ensure intensive absorption of nitric acid from water and pH 25 maintenance in a slightly acid area. (authors)

Water chemistry at RBMK plants: Problems and solutions

Energy Technology Data Exchange (ETDEWEB)

Mamet, V.; Yurmanov, V. [VNIIAES (Russian Federation)

2002-07-01

After around 15 years of operation RBMK-1000 units undergo a major refit, which includes safety system upgrading, fuel tube replacement, etc. The above upgrading has created problems for water chemistry. In particular, in late 80's in-core insertion time of the portion of control rods was reduced 10-fold thanks to a transfer from water to filming cooling of scram channels. Scram channels are cooled with inner surface water film cooling and nitrogen is injected into heads via special pipelines. Such cooling system modernization ensures fast insertion of absorber rods. The above upgrade intensified nitric acid radiolytic generation in water coolant and pH{sub 25} value shift to acid conditions (up to 4.5). The results of corrosion tests in such conditions proved the necessity to improve water chemistry to ensure corrosion protection of scram/control rod and circuit components, especially those made out of aluminium alloy. Since 1990 the new revision of the RBMK-1000 water chemistry standard specified the new normal operational limit and action levels for possible temporary deviations of pH{sub 25} value. RBMK plant specific measures were implemented at RBMK plants to meet the above requirements of the 1990 revision of the RBMK-1000 water chemistry standard. Clean-up systems of the above circuit were upgraded to ensure intensive absorption of nitric acid from water and pH{sub 25} maintenance in a slightly acid area. (authors)

Influence of water chemistry on fuel cladding behaviour. Proceedings of a technical committee meeting

International Nuclear Information System (INIS)

1997-02-01

For the purpose of the meeting water chemistry included the actual practice, the water chemistry monitoring and the on-going research. Corrosion included also hydriding, recent observations made in reactors, modelling and the recent research carried out. Fifty seven participants representing twenty countries attended the thirty formal presentations and the subsequent discussions. The thirty papers presented were split into five sessions covering, Reactor experience, Mechanism and Modelling, Oxidation and hydriding, On-line monitoring of water chemistry and the review of existing and advanced water chemistries. Four panel discussions including ''Corrosion mechanism and Modelling'', ''Corrosion and Hydriding'', ''Plant Experience and Loop Experiments'', Water Chemistry, Current Practice and Emerging Solutions'' and ''On-line Monitoring of Water Chemistry and Corrosion'' were organized. The main points of discussion focussed on the optimization of water chemistry, the compatibility of potassium water chemistry with the utilization of Zircaloy 4 or the utilization of zirconium niobium cladding with lithium water chemistry. The effect of the fabrication route and of the cladding composition (Sn content) on the corrosion kinetics, the state of the art and the correlative gaps in cladding corrosion modelling and the recent developments of on-line monitoring of water chemistry together with examination of suitable developments, were also discussed. Refs, figs, tabs

Influence of water chemistry on fuel cladding behaviour. Proceedings of a technical committee meeting

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-02-01

For the purpose of the meeting water chemistry included the actual practice, the water chemistry monitoring and the on-going research. Corrosion included also hydriding, recent observations made in reactors, modelling and the recent research carried out. Fifty seven participants representing twenty countries attended the thirty formal presentations and the subsequent discussions. The thirty papers presented were split into five sessions covering, Reactor experience, Mechanism and Modelling, Oxidation and hydriding, On-line monitoring of water chemistry and the review of existing and advanced water chemistries. Four panel discussions including ``Corrosion mechanism and Modelling``, ``Corrosion and Hydriding``, ``Plant Experience and Loop Experiments``, Water Chemistry, Current Practice and Emerging Solutions`` and ``On-line Monitoring of Water Chemistry and Corrosion`` were organized. The main points of discussion focussed on the optimization of water chemistry, the compatibility of potassium water chemistry with the utilization of Zircaloy 4 or the utilization of zirconium niobium cladding with lithium water chemistry. The effect of the fabrication route and of the cladding composition (Sn content) on the corrosion kinetics, the state of the art and the correlative gaps in cladding corrosion modelling and the recent developments of on-line monitoring of water chemistry together with examination of suitable developments, were also discussed. Refs, figs, tabs.

The chemistry of plutonium revealed

International Nuclear Information System (INIS)

Connick, R.E.

1990-01-01

In 1941 one goal of the Manhattan Project was to unravel the chemistry of the synthetic element plutonium as rapidly as possible. Important insights were obtained from tracer experiments, but the full complexity of plutonium chemistry was not revealed until macroscopic amounts (milligrams) became available. Because processes for separation from fission products were aqueous solution based, such solution chemistry was emphasized, particularly precipitation and oxidation-reduction behavior. The latter turned out to be unusually intricate when it was discovered that two more oxidation states existed in aqueous solution than had previously been suspected. Further, it was found that an equilibrium was rapidly established among the four aqueous oxidation states while at the same time any three were not in equilibrium. These and other observations made while doing a crash study of a previously unknown element will be reported

Ion binding by humic and fulvic acids: A computational procedure based on functional site heterogeneity and the physical chemistry of polyelectrolyte solutions

International Nuclear Information System (INIS)

Marinsky, J.A.; Reddy, M.M.; Ephraim, J.; Mathuthu, A.

1988-04-01

Ion binding equilibria for humic and fulvic acids are examined from the point of view of functional site heterogeneity and the physical chemistry of polyelectrolyte solutions. A detailed explanation of the potentiometric properties of synthetic polyelectrolytes and ion-exchange gels is presented first to provide the basis for a parallel consideration of the potentiometric properties exhibited by humic and fulvic acids. The treatment is then extended to account for functional site heterogeneity. Sample results are presented for analysis of the ion-binding reactions of a standard soil fulvic acid (Armadale Horizons Bh) with this approach to test its capability for anticipation of metal ion removal from solution. The ultimate refined model is shown to be adaptable, after appropriate consideration of the heterogeneity and polyelectrolyte factors, to programming already available for the consideration of ion binding by inorganics in natural waters. (orig.)

Coupled effects of solution chemistry and hydrodynamics on the mobility and transport of quantum dot nanomaterials in the Vadose Zone

Science.gov (United States)

To investigate the coupled effects of solution chemistry and vadose zone processes on the mobility of quantum dot (QD) nanoparticles, laboratory scale transport experiments were performed. The complex coupled effects of ionic strength, size of QD aggregates, surface tension, contact angle, infiltrat...

Effect of wood ash application on soil solution chemistry of tropical acid soils: incubation study.

Science.gov (United States)

Nkana, J C Voundi; Demeyer, A; Verloo, M G

2002-12-01

The objective of this study was to determine the effect of wood ash application on soil solution composition of three tropical acid soils. Calcium carbonate was used as a reference amendment. Amended soils and control were incubated for 60 days. To assess soluble nutrients, saturation extracts were analysed at 15 days intervals. Wood ash application affects the soil solution chemistry in two ways, as a liming agent and as a supplier of nutrients. As a liming agent, wood ash application induced increases in soil solution pH, Ca, Mg, inorganic C, SO4 and DOC. As a supplier of elements, the increase in the soil solution pH was partly due to ligand exchange between wood ash SO4 and OH- ions. Large increases in concentrations of inorganic C, SO4, Ca and Mg with wood ash relative to lime and especially increases in K reflected the supply of these elements by wood ash. Wood ash application could represent increased availability of nutrients for the plant. However, large concentrations of basic cations, SO4 and NO3 obtained with higher application rates could be a concern because of potential solute transport to surface waters and groundwater. Wood ash must be applied at reasonable rates to avoid any risk for the environment.

Effects of `Environmental Chemistry' Elective Course Via Technology-Embedded Scientific Inquiry Model on Some Variables

Science.gov (United States)

Çalik, Muammer; Özsevgeç, Tuncay; Ebenezer, Jazlin; Artun, Hüseyin; Küçük, Zeynel

2014-06-01

The purpose of this study is to examine the effects of `environmental chemistry' elective course via Technology-Embedded Scientific Inquiry (TESI) model on senior science student teachers' (SSSTs) conceptions of environmental chemistry concepts/issues, attitudes toward chemistry, and technological pedagogical content knowledge (TPACK) levels. Within one group pre-test-post-test design, the study was conducted with 117 SSSTs (68 females and 49 males—aged 21-23 years) enrolled in an `environmental chemistry' elective course in the spring semester of 2011-2012 academic-years. Instruments for data collection comprised of Environmental Chemistry Conceptual Understanding Questionnaire, TPACK survey, and Chemistry Attitudes and Experiences Questionnaire. Significant increases in the SSSTs' conceptions of environmental chemistry concepts/issues, attitudes toward chemistry, and TPACK levels are attributed to the SSSTs learning how to use the innovative technologies in the contexts of the `environmental chemistry' elective course and teaching practicum. The study implies that the TESI model may serve a useful purpose in experimental science courses that use the innovative technologies. However, to generalize feasibility of the TESI model, it should be evaluated with SSSTs in diverse learning contexts.

The GEOS Chemistry Climate Model: Comparisons to Satellite Data

Science.gov (United States)

Stolarski, R. S.; Douglass, A. R.

2008-05-01

The Goddard Earth Observing System Chemistry Climate Model (GEOS CCM) has been developed by combining the atmospheric chemistry and transport modules developed over the years at Goddard and the GEOS general circulation model, also developed at Goddard. We will compare model simulations of ozone, and the minor constituents that affect ozone, for the period around 1980 with newly released revised data from the Limb Infrared Monitor of the Stratosphere (LIMS) instrument on Nimbus 4. We will also compare model simulations for the period of the early 2000s with the data from the Microwave Limb Sounder (MLS) and the High Resolution Dynamic Limb Sounder (HRDLS) on the Aura satellite. We will use these comparisons to examine the performance of the model for the present atmosphere and for the change that has occurred during the last 2 decades of ozone loss due to chlorine and bromine compounds released from chlorofluorocarbons and halons.

Chemistry in Microfluidic Channels

Science.gov (United States)

Chia, Matthew C.; Sweeney, Christina M.; Odom, Teri W.

2011-01-01

General chemistry introduces principles such as acid-base chemistry, mixing, and precipitation that are usually demonstrated in bulk solutions. In this laboratory experiment, we describe how chemical reactions can be performed in a microfluidic channel to show advanced concepts such as laminar fluid flow and controlled precipitation. Three sets of…

Recent studies of uranium and plutonium chemistry in alkaline radioactive waste solutions

International Nuclear Information System (INIS)

King, William D.; Wilmarth, William R.; Hobbs, David T.; Edwards, Thomas B.

2008-01-01

Solubility studies of uranium and plutonium in a caustic, radioactive Savannah River Site tank waste solution revealed the existence of uranium supersaturation in the as-received sample. Comparison of the results to predictions generated from previously published models for solubility in these waste types revealed that the U model poorly predicts solubility while Pu model predictions are quite consistent with experimental observations. Separate studies using simulated Savannah River Site evaporator feed solution revealed that the known formation of sodium aluminosilicate solids in waste evaporators can promote rapid precipitation of uranium from supersaturated solutions

Frontiers in Atmospheric Chemistry Modelling

Science.gov (United States)

Colette, Augustin; Bessagnet, Bertrand; Meleux, Frederik; Rouïl, Laurence

2013-04-01

The first pan-European kilometre-scale atmospheric chemistry simulation is introduced. The continental-scale air pollution episode of January 2009 is modelled with the CHIMERE offline chemistry-transport model with a massive grid of 2 million horizontal points, performed on 2000 CPU of a high performance computing system hosted by the Research and Technology Computing Center at the French Alternative Energies and Atomic Energy Commission (CCRT/CEA). Besides the technical challenge, which demonstrated the robustness of the selected air quality model, we discuss the added value in terms of air pollution modelling and decision support. The comparison with in-situ observations shows that model biases are significantly improved despite some spurious added spatial variability attributed to shortcomings in the emission downscaling process and coarse resolution of the meteorological fields. The increased spatial resolution is clearly beneficial for the detection of exceedances and exposure modelling. We reveal small scale air pollution patterns that highlight the contribution of city plumes to background air pollution levels. Up to a factor 5 underestimation of the fraction of population exposed to detrimental levels of pollution can be obtained with a coarse simulation if subgrid scale correction such as urban increments are ignored. This experiment opens new perspectives for environmental decision making. After two decades of efforts to reduce air pollutant emissions across Europe, the challenge is now to find the optimal trade-off between national and local air quality management strategies. While the first approach is based on sectoral strategies and energy policies, the later builds upon new alternatives such as urban development. The strategies, the decision pathways and the involvement of individual citizen differ, and a compromise based on cost and efficiency must be found. We illustrated how high performance computing in atmospheric science can contribute to this

Theoretical chemistry periodicities in chemistry and biology

CERN Document Server

Eyring, Henry

1978-01-01

Theoretical Chemistry: Periodicities in Chemistry and Biology, Volume 4 covers the aspects of theoretical chemistry. The book discusses the stably rotating patterns of reaction and diffusion; the chemistry of inorganic systems exhibiting nonmonotonic behavior; and population cycles. The text also describes the mathematical modeling of excitable media in neurobiology and chemistry; oscillating enzyme reactions; and oscillatory properties and excitability of the heart cell membrane. Selected topics from the theory of physico-chemical instabilities are also encompassed. Chemists, mechanical engin

Climate effects of anthropogenic sulfate: Simulations from a coupled chemistry/climate model

International Nuclear Information System (INIS)

Chuang, C.C.; Penner, J.E.; Taylor, K.E.; Walton, J.J.

1993-09-01

In this paper, we use a more comprehensive approach by coupling a climate model with a 3-D global chemistry model to investigate the forcing by anthropogenic aerosol sulfate. The chemistry model treats the global-scale transport, transformation, and removal of SO 2 , DMS and H 2 SO 4 species in the atmosphere. The mass concentration of anthropogenic sulfate from fossil fuel combustion and biomass burning is calculated in the chemistry model and provided to the climate model where it affects the shortwave radiation. We also investigate the effect, with cloud nucleation parameterized in terms of local aerosol number, sulfate mass concentration and updraft velocity. Our simulations indicate that anthropogenic sulfate may result in important increases in reflected solar radiation, which would mask locally the radiative forcing from increased greenhouse gases. Uncertainties in these results will be discussed

Modelling with the master equation solution methods and applications in social and natural sciences

CERN Document Server

Haag, Günter

2017-01-01

This book presents the theory and practical applications of the Master equation approach, which provides a powerful general framework for model building in a variety of disciplines. The aim of the book is to not only highlight different mathematical solution methods, but also reveal their potential by means of practical examples. Part I of the book, which can be used as a toolbox, introduces selected statistical fundamentals and solution methods for the Master equation. In Part II and Part III, the Master equation approach is applied to important applications in the natural and social sciences. The case studies presented mainly hail from the social sciences, including urban and regional dynamics, population dynamics, dynamic decision theory, opinion formation and traffic dynamics; however, some applications from physics and chemistry are treated as well, underlining the interdisciplinary modelling potential of the Master equation approach. Drawing upon the author’s extensive teaching and research experience...

In-Package Chemistry Abstraction

Energy Technology Data Exchange (ETDEWEB)

P.S. Domski

2003-07-21

The work associated with the development of this model report was performed in accordance with the requirements established in ''Technical Work Plan for Waste Form Degradation Modeling, Testing, and Analyses in Support of SR and LA'' (BSC 2002a). The in-package chemistry model and in-package chemistry model abstraction are developed to predict the bulk chemistry inside of a failed waste package and to provide simplified expressions of that chemistry. The purpose of this work is to provide the abstraction model to the Performance Assessment Project and the Waste Form Department for development of geochemical models of the waste package interior. The scope of this model report is to describe the development and validation of the in-package chemistry model and in-package chemistry model abstraction. The in-package chemistry model will consider chemical interactions of water with the waste package materials and the waste form for commercial spent nuclear fuel (CSNF) and codisposed high-level waste glass (HLWG) and N Reactor spent fuel (CDNR). The in-package chemistry model includes two sub-models, the first a water vapor condensation (WVC) model, where water enters a waste package as vapor and forms a film on the waste package components with subsequent film reactions with the waste package materials and waste form--this is a no-flow model, the reacted fluids do not exit the waste package via advection. The second sub-model of the in-package chemistry model is the seepage dripping model (SDM), where water, water that may have seeped into the repository from the surrounding rock, enters a failed waste package and reacts with the waste package components and waste form, and then exits the waste package with no accumulation of reacted water in the waste package. Both of the submodels of the in-package chemistry model are film models in contrast to past in-package chemistry models where all of the waste package pore space was filled with water. The

In-Package Chemistry Abstraction

International Nuclear Information System (INIS)

P.S. Domski

2003-01-01

The work associated with the development of this model report was performed in accordance with the requirements established in ''Technical Work Plan for Waste Form Degradation Modeling, Testing, and Analyses in Support of SR and LA'' (BSC 2002a). The in-package chemistry model and in-package chemistry model abstraction are developed to predict the bulk chemistry inside of a failed waste package and to provide simplified expressions of that chemistry. The purpose of this work is to provide the abstraction model to the Performance Assessment Project and the Waste Form Department for development of geochemical models of the waste package interior. The scope of this model report is to describe the development and validation of the in-package chemistry model and in-package chemistry model abstraction. The in-package chemistry model will consider chemical interactions of water with the waste package materials and the waste form for commercial spent nuclear fuel (CSNF) and codisposed high-level waste glass (HLWG) and N Reactor spent fuel (CDNR). The in-package chemistry model includes two sub-models, the first a water vapor condensation (WVC) model, where water enters a waste package as vapor and forms a film on the waste package components with subsequent film reactions with the waste package materials and waste form--this is a no-flow model, the reacted fluids do not exit the waste package via advection. The second sub-model of the in-package chemistry model is the seepage dripping model (SDM), where water, water that may have seeped into the repository from the surrounding rock, enters a failed waste package and reacts with the waste package components and waste form, and then exits the waste package with no accumulation of reacted water in the waste package. Both of the submodels of the in-package chemistry model are film models in contrast to past in-package chemistry models where all of the waste package pore space was filled with water. The current in

Modelling neutral and plasma chemistry with DSMC

International Nuclear Information System (INIS)

Bartel, Timothy J.

2003-01-01

The Direct Simulation Monte Carlo (DSMC) method is a powerful method for modelling chemically reacting flows. It is a statistical method which simulates the Boltzmann equation by interacting computational particles which represent a large number of a single species type. A statistical problem will occur when trace concentrations are required to be accurately modelled; the traditional strategy is to use more computational particles per cell or simply obtain lower statistics and thus have higher uncertainty for the trace concentrations. A new method, cell based chemistry (CBC), based on an integral balancing concept, allows all chemistry, including trace reactions, to be efficiently modelled in the framework of DSMC. This strategy first separates the collision phase from the reacting phase. Then a strategy is presented which conserves both the collision and reaction frequencies in a consistent manner. The illustrative problem is a chemically reacting glow discharge plasma; the ion concentrations typically are at a 0.1% mole fraction but dominant the physical mechanism of the system. Comparisons will be made to a chlorine plasma in a Gaseous Electronics Conference (GEC) reference cell with an inductive coil at approximately 20 mtorr system pressure

Underlying chemistry research for the nuclear fuel waste management program

International Nuclear Information System (INIS)

Torgerson, D.F.; Sagert, N.H.; Shoesmith, D.W.; Taylor, P.

1984-04-01

This document reviews the underlying chemistry research part of the Canadian Nuclear Fuel Waste Management Program, carried out in the Research Chemistry Branch. This research is concerned with developing the basic chemical knowledge and under-standing required in other parts of the Program. There are four areas of underlying research: Waste Form Chemistry, Solute and Solution Chemistry, Rock-Water-Waste Interactions, and Abatement and Monitoring of Gas-Phase Radionuclides

Modeling nitrogen chemistry in combustion

DEFF Research Database (Denmark)

Glarborg, Peter; Miller, James A.; Ruscic, Branko

2018-01-01

the accuracy of engineering calculations and thereby the potential of primary measures for NOx control. In this review our current understanding of the mechanisms that are responsible for combustion-generated nitrogen-containing air pollutants is discussed. The thermochemistry of the relevant nitrogen...... via NNH or N2O are discussed, along with the chemistry of NO removal processes such as reburning and Selective Non-Catalytic Reduction of NO. Each subset of the mechanism is evaluated against experimental data and the accuracy of modeling predictions is discussed....

Dynamic-chemistry-aerosol modelling interaction: the ESCOMPTE 2001 experiment

International Nuclear Information System (INIS)

Cousin, F.

2004-09-01

After most pollution studies independently devoted to gases and aerosols, there now appears an urgent need to consider their interactions. In this view, an aerosol module has been implemented in the Meso-NH-C model to simulate two IOPs documented during the ESCOMPTE campaign which took place in the Marseille/Fos-Berre region in June-July 2001. First, modelled dynamic parameters (winds, temperatures, boundary layer thickness) and gaseous chemistry have been validated with measurements issued from the exhaustive ESCOMPTE database. Sensitivity analysis have also been performed using different gaseous emission inventories at various resolution. These simulations have illustrated the deep impact of both synoptic and local dynamics on observed ozone concentrations on June 24 (IOP2b) in the ESCOMPTE domain. Afterwards, the ORISAM aerosol module has been introduced into the Meso-NH-C model. Dynamics, gaseous chemistry and aerosol processes have thus been coupled on-line. The particulate pollution episode on June 24 (IOP2b) has been characterised through a satisfactory comparison, specially from sub-micron particles, between modelling and measurements at different representative stations in the domain. This study, with validation of the particulate emission inventory has also highlighted the need for future improvements, such as further characterisation of organic and inorganic aerosol species and consideration of coarse particles. Aerosol impact on gaseous chemistry has been preliminary approached in view of future development and modification to be given to the Meso-NH-C model. (author)

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

Science.gov (United States)

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-01-01

“Clumped-isotope” thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope “clumps”). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals.We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect.Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3− and CO32−. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

Science.gov (United States)

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-10-01

;Clumped-isotope; thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope ;clumps;). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals. We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect. Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3- and CO32-. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two

Combustion chemistry of alcohols: Experimental and modeled structure of a premixed 2-methylbutanol flame

KAUST Repository

Lucassen, Arnas

2014-06-14

This paper presents a detailed investigation of 2-methylbutanol combustion chemistry in low-pressure premixed flames. This chemistry is of particular interest to study because this compound is potentially a lignocellulosic-based, next-generation biofuel. The detailed chemical structure of a stoichiometric low-pressure (25 Torr) flame was determined using flame-sampling molecular-beam mass spectrometry. A total of 55 species were identified and subsequently quantitative mole fraction profiles as function of distance from the burner surface were determined. In an independent effort, a detailed flame chemistry model for 2-methylbutanol was assembled based on recent knowledge gained from combustion chemistry studies for butanol isomers ([Sarathy et al. Combust. Flame 159 (6) (2012) 2028-2055]) and iso-pentanol (3-methylbutanol) [Sarathy et al. Combust. Flame 160 (12) (2013) 2712-2728]. Experimentally determined and modeled mole fraction profiles were compared to demonstrate the model\\'s capabilities. Examples of individual mole fraction profiles are discussed together with the most significant fuel consumption pathways to highlight the combustion chemistry of 2-methylbutanol. Discrepancies between experimental and modeling results are used to suggest areas where improvement of the kinetic model would be needed. © 2014.

Plutonium chemistry: a synthesis of experimental data and a quantitative model for plutonium oxide solubility

International Nuclear Information System (INIS)

Haschke, J.M.; Oversby, V.M.

2002-01-01

The chemistry of plutonium is important for assessing potential behavior of radioactive waste under conditions of geologic disposal. This paper reviews experimental data on dissolution of plutonium oxide solids, describes a hybrid kinetic-equilibrium model for predicting steady-state Pu concentrations, and compares laboratory results with predicted Pu concentrations and oxidation-state distributions. The model is based on oxidation of PuO 2 by water to produce PuO 2+x , an oxide that can release Pu(V) to solution. Kinetic relationships between formation of PuO 2+x , dissolution of Pu(V), disproportionation of Pu(V) to Pu(IV) and Pu(VI), and reduction of Pu(VI) are given and used in model calculations. Data from tests of pyrochemical salt wastes in brines are discussed and interpreted using the conceptual model. Essential data for quantitative modeling at conditions relevant to nuclear waste repositories are identified and laboratory experiments to determine rate constants for use in the model are discussed

Life's Biological Chemistry: A Destiny or Destination Starting from Prebiotic Chemistry?

Science.gov (United States)

Krishnamurthy, Ramanarayanan

2018-06-05

Research into understanding the origins -and evolution- of life has long been dominated by the concept of taking clues from extant biology and extrapolating its molecules and pathways backwards in time. This approach has also guided the search for solutions to the problem of how contemporary biomolecules would have arisen directly from prebiotic chemistry on early earth. However, the continuing difficulties in finding universally convincing solutions in connecting prebiotic chemistry to biological chemistry should give us pause, and prompt us to rethink this concept of treating extant life's chemical processes as the sole end goal and, therefore, focusing only -and implicitly- on the respective extant chemical building blocks. Rather, it may be worthwhile "to set aside the goal" and begin with what would have been plausible prebiotic reaction mixtures (which may have no obvious or direct connection to life's chemical building blocks and processes) - and allow their chemistries and interactions, under different geochemical constraints, to guide and illuminate as to what processes and systems can emerge. Such a conceptual approach gives rise to the prospect that chemistry of life-as-we-know-it is not the only result (not a "destiny"), but one that has emerged among many potential possibilities (a "destination"). This postulate, in turn, could impact the way we think about chemical signatures and criteria used in the search for alternative and extraterrestrial "life". As a bonus, we may discover the chemistries and pathways naturally that led to the emergence of life as we know it. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Principles of quantum chemistry

CERN Document Server

George, David V

2013-01-01

Principles of Quantum Chemistry focuses on the application of quantum mechanics in physical models and experiments of chemical systems.This book describes chemical bonding and its two specific problems - bonding in complexes and in conjugated organic molecules. The very basic theory of spectroscopy is also considered. Other topics include the early development of quantum theory; particle-in-a-box; general formulation of the theory of quantum mechanics; and treatment of angular momentum in quantum mechanics. The examples of solutions of Schroedinger equations; approximation methods in quantum c

Chemistry Division : Annual progress report of 1974

International Nuclear Information System (INIS)

1974-01-01

Research and development activities (during 1974) of the Chemistry Division of the Bhabha Atomic Research Centre, Bombay, are described. Some of the activities of particular interest to nuclear science and technology are: (1) chemistry-based problems of the operating power reactors such as development of a decontaminating solution for power reactors, correlation of iodine-131 levels in the primary heat transport system of a reactor with its operation (2) release of fission gases like xenon from ceramic fuels and (3) radiation chemistry of nitrate solutions (M.G.B.)

Novel bi-metallic uranyl complexes - Redox chemistry in aqueous solutions

International Nuclear Information System (INIS)

Yardeni, A.; Mizrahi, E.; Maimon, I.; Zilbermann, G.; Meyerstein, D.; Zehavi-cohen, A.Z.

2014-01-01

The synthesis of organic ligands which can accommodate two uranium atoms at different oxidation states, mixed valency being then achieved by redox chemistry at room temperature is definitely a challenge in coordination chemistry. The following complexes were synthesized and characterized by elemental analysis, NMR, MS, IR and UV-vis

Model for diffusion and porewater chemistry in compacted bentonite. Theoretical basis and the solution methodology for the transport model

International Nuclear Information System (INIS)

Lehikoinen, J.

1997-01-01

This report describes the progress of the computer model for ionic transport in bentonite. The research is part of the project Microstructural and chemical parameters of bentonite as determinants of waste isolation efficiency within the Nuclear fission safety program organized by The Commission of the European Communities. The study was started by collecting a comprehensive body of available data on space-charge transport modelling and creating a conceptualization of the problem at hand. The numerical discretization of the governing equations by finite differences was also initiated. This report introduces the theoretical basis for the model, somewhat more elaborated than presented in Progress Report 1/1996, and rectifies a few mistakes appearing in that report. It also gives a brief introduction to the solution methodology of the disc retized governing equations. (orig.) (12 refs.)

Description and Evaluation of IAP-AACM: A Global-regional Aerosol Chemistry Model for the Earth System Model CAS-ESM

Science.gov (United States)

Wei, Y.; Chen, X.

2017-12-01

We present a first description and evaluation of the IAP Atmospheric Aerosol Chemistry Model (IAP-AACM) which has been integrated into the earth system model CAS-ESM. In this way it is possible to research into interaction of clouds and aerosol by its two-way coupling with the IAP Atmospheric General Circulation Model (IAP-AGCM). The model has a nested global-regional grid based on the Global Environmental Atmospheric Transport Model (GEATM) and the Nested Air Quality Prediction Modeling System (NAQPMS). The AACM provides two optional gas chemistry schemes, the CBM-Z gas chemistry as well as a sulfur oxidize box designed specifically for the CAS-ESM. Now the model driven by AGCM has been applied to a 1-year simulation of tropospheric chemistry both on global and regional scales for 2014, and been evaluated against various observation datasets, including aerosol precursor gas concentration, aerosol mass and number concentrations. Furthermore, global budgets in AACM are compared with other global aerosol models. Generally, the AACM simulations are within the range of other global aerosol model predictions, and the model has a reasonable agreement with observations of gases and particles concentration both on global and regional scales.

The Chemistry of Atmosphere-Forest Exchange (CAFE Model – Part 1: Model description and characterization

Directory of Open Access Journals (Sweden)

G. M. Wolfe

2011-01-01

Full Text Available We present the Chemistry of Atmosphere-Forest Exchange (CAFE model, a vertically-resolved 1-D chemical transport model designed to probe the details of near-surface reactive gas exchange. CAFE integrates all key processes, including turbulent diffusion, emission, deposition and chemistry, throughout the forest canopy and mixed layer. CAFE utilizes the Master Chemical Mechanism (MCM and is the first model of its kind to incorporate a suite of reactions for the oxidation of monoterpenes and sesquiterpenes, providing a more comprehensive description of the oxidative chemistry occurring within and above the forest. We use CAFE to simulate a young Ponderosa pine forest in the Sierra Nevada, CA. Utilizing meteorological constraints from the BEARPEX-2007 field campaign, we assess the sensitivity of modeled fluxes to parameterizations of diffusion, laminar sublayer resistance and radiation extinction. To characterize the general chemical environment of this forest, we also present modeled mixing ratio profiles of biogenic hydrocarbons, hydrogen oxides and reactive nitrogen. The vertical profiles of these species demonstrate a range of structures and gradients that reflect the interplay of physical and chemical processes within the forest canopy, which can influence net exchange.

Results of an interactively coupled atmospheric chemistry - general circulation model. Comparison with observations

Energy Technology Data Exchange (ETDEWEB)

Hein, R.; Dameris, M.; Schnadt, C. [and others

2000-01-01

An interactively coupled climate-chemistry model which enables a simultaneous treatment of meteorology and atmospheric chemistry and their feedbacks is presented. This is the first model, which interactively combines a general circulation model based on primitive equations with a rather complex model of stratospheric and tropospheric chemistry, and which is computational efficient enough to allow long-term integrations with currently available computer resources. The applied model version extends from the Earth's surface up to 10 hPa with a relatively high number (39) of vertical levels. We present the results of a present-day (1990) simulation and compare it to available observations. We focus on stratospheric dynamics and chemistry relevant to describe the stratospheric ozone layer. The current model version ECHAM4.L39(DLR)/CHEM can realistically reproduce stratospheric dynamics in the Arctic vortex region, including stratospheric warming events. This constitutes a major improvement compared to formerly applied model versions. However, apparent shortcomings in Antarctic circulation and temperatures persist. The seasonal and interannual variability of the ozone layer is simulated in accordance with observations. Activation and deactivation of chlorine in the polar stratospheric vortices and their interhemispheric differences are reproduced. The consideration of the chemistry feedback on dynamics results in an improved representation of the spatial distribution of stratospheric water vapor concentrations, i.e., the simulated meriodional water vapor gradient in the stratosphere is realistic. The present model version constitutes a powerful tool to investigate, for instance, the combined direct and indirect effects of anthropogenic trace gas emissions, and the future evolution of the ozone layer. (orig.)

Using Transport Diagnostics to Understand Chemistry Climate Model Ozone Simulations

Science.gov (United States)

Strahan, S. E.; Douglass, A. R.; Stolarski, R. S.; Akiyoshi, H.; Bekki, S.; Braesicke, P.; Butchart, N.; Chipperfield, M. P.; Cugnet, D.; Dhomse, S.;

Disciplines, models, and computers: the path to computational quantum chemistry.

Science.gov (United States)

Lenhard, Johannes

2014-12-01

Many disciplines and scientific fields have undergone a computational turn in the past several decades. This paper analyzes this sort of turn by investigating the case of computational quantum chemistry. The main claim is that the transformation from quantum to computational quantum chemistry involved changes in three dimensions. First, on the side of instrumentation, small computers and a networked infrastructure took over the lead from centralized mainframe architecture. Second, a new conception of computational modeling became feasible and assumed a crucial role. And third, the field of computa- tional quantum chemistry became organized in a market-like fashion and this market is much bigger than the number of quantum theory experts. These claims will be substantiated by an investigation of the so-called density functional theory (DFT), the arguably pivotal theory in the turn to computational quantum chemistry around 1990.

Combustion chemistry of alcohols: Experimental and modeled structure of a premixed 2-methylbutanol flame

KAUST Repository

Lucassen, Arnas; Park, Sungwoo; Hansen, Nils; Sarathy, Mani

2014-01-01

This paper presents a detailed investigation of 2-methylbutanol combustion chemistry in low-pressure premixed flames. This chemistry is of particular interest to study because this compound is potentially a lignocellulosic-based, next-generation biofuel. The detailed chemical structure of a stoichiometric low-pressure (25 Torr) flame was determined using flame-sampling molecular-beam mass spectrometry. A total of 55 species were identified and subsequently quantitative mole fraction profiles as function of distance from the burner surface were determined. In an independent effort, a detailed flame chemistry model for 2-methylbutanol was assembled based on recent knowledge gained from combustion chemistry studies for butanol isomers ([Sarathy et al. Combust. Flame 159 (6) (2012) 2028-2055]) and iso-pentanol (3-methylbutanol) [Sarathy et al. Combust. Flame 160 (12) (2013) 2712-2728]. Experimentally determined and modeled mole fraction profiles were compared to demonstrate the model's capabilities. Examples of individual mole fraction profiles are discussed together with the most significant fuel consumption pathways to highlight the combustion chemistry of 2-methylbutanol. Discrepancies between experimental and modeling results are used to suggest areas where improvement of the kinetic model would be needed. © 2014.

An abstraction layer for efficient memory management of tabulated chemistry and flamelet solutions

Science.gov (United States)

Weise, Steffen; Messig, Danny; Meyer, Bernd; Hasse, Christian

2013-06-01

A large number of methods for simulating reactive flows exist, some of them, for example, directly use detailed chemical kinetics or use precomputed and tabulated flame solutions. Both approaches couple the research fields computational fluid dynamics and chemistry tightly together using either an online or offline approach to solve the chemistry domain. The offline approach usually involves a method of generating databases or so-called Lookup-Tables (LUTs). As these LUTs are extended to not only contain material properties but interactions between chemistry and turbulent flow, the number of parameters and thus dimensions increases. Given a reasonable discretisation, file sizes can increase drastically. The main goal of this work is to provide methods that handle large database files efficiently. A Memory Abstraction Layer (MAL) has been developed that handles requested LUT entries efficiently by splitting the database file into several smaller blocks. It keeps the total memory usage at a minimum using thin allocation methods and compression to minimise filesystem operations. The MAL has been evaluated using three different test cases. The first rather generic one is a sequential reading operation on an LUT to evaluate the runtime behaviour as well as the memory consumption of the MAL. The second test case is a simulation of a non-premixed turbulent flame, the so-called HM1 flame, which is a well-known test case in the turbulent combustion community. The third test case is a simulation of a non-premixed laminar flame as described by McEnally in 1996 and Bennett in 2000. Using the previously developed solver 'flameletFoam' in conjunction with the MAL, memory consumption and the performance penalty introduced were studied. The total memory used while running a parallel simulation was reduced significantly while the CPU time overhead associated with the MAL remained low.

Chemistry and physics

International Nuclear Information System (INIS)

Broerse, J.J.; Barendsen, G.W.; Kal, H.B.; Kogel, A.J. van der

1983-01-01

This book contains the extended abstracts of the contributions of the poster workshop sessions on chemistry and physics of the 7th international congress of radiation research. They cover the following main topics: primary processes in radiation physics and chemistry, general chemistry in radiation chemistry, DNA and model systems in radiation chemistry, molecules of biological interest in radiation chemistry, techniques in radiation chemistry, hot atom chemistry. refs.; figs.; tabs

Theory, modeling, and simulation annual report, 1992

Energy Technology Data Exchange (ETDEWEB)

1993-05-01

This report briefly discusses research on the following topics: development of electronic structure methods; modeling molecular processes in clusters; modeling molecular processes in solution; modeling molecular processes in separations chemistry; modeling interfacial molecular processes; modeling molecular processes in the atmosphere; methods for periodic calculations on solids; chemistry and physics of minerals; graphical user interfaces for computational chemistry codes; visualization and analysis of molecular simulations; integrated computational chemistry environment; and benchmark computations.

Chemistry of the actinide elements. Second edition

International Nuclear Information System (INIS)

Katz, J.J.; Seaborg, G.T.; Morss, L.R.

1987-01-01

This is an exhaustive, updated discourse on the chemistry of Actinides, Volume 1 contains a systematic coverage of the elements Ac, Th, Pa, U, Np, and Pu, which constitutes Part 1 of the work. The characterization of each element is discussed in terms of its nuclear properties, occurrence, preparation, atomic and metallic properties, chemistry of specific compounds, and solution chemistry. The first part of Volume 2 follows the same format as Volume 1 but is confined to the elements Am, Cm, Bk, Cf, and Es, plus a more condensed coverage of the Transeinsteinium elements (Fm, Md, No, Lw, and 104-109). Part 2 of this volume is devoted to a discussion of the actinide elements in general, with a specific focus on electronic spectra, thermodynamic and magnetic properties, the metallic state, structural chemistry, solution kinetics, organometallic chemistry for σ- and π-bonded compounds, and some concluding remarks on the superheavy elements

Radiation chemistry of the liquid state

International Nuclear Information System (INIS)

Buxton, G.V.

1987-01-01

More is known about the radiation chemistry of water than any other liquid. From a practical viewpoint out knowledge is virtually complete, and water radiolysis now provides a very convenient way of generating an enormous variety of unstable species under well-defined conditions. This facility, coupled with the techniques of pulse radiolysis, has opened up new areas in aqueous inorganic, organic, and biochemistry that cannot be readily studied by thermal or photochemical methods. This chapter is aimed, therefore, at those who wish to use radiolytic methods to generate and study unstable species in aqueous solution. The basic features of the radiation chemistry of water are described first to show how the primary radical and molecular products evolve with time and to delineate the bounds of useful experimental conditions. Next, the properties of the primary radicals are summarized, and examples are given to show how the primary radicals can be converted into secondary radicals, often of a single kind. This is an important aspect of the radiation chemistry of aqueous solutions. Lastly, the impact of our knowledge of the radiation chemistry of water on advances in general chemistry is illustrated by examples from the fields of inorganic and organic chemistry

Meso-scale modeling of air pollution transport/chemistry/deposition and its application

International Nuclear Information System (INIS)

Kitada, Toshihiro

2007-01-01

Transport/chemistry/deposition model for atmospheric trace chemical species is now regarded as an important tool for an understanding of the effects of various human activities, such as fuel combustion and deforestation, on human health, eco-system, and climate and for planning of appropriate control of emission sources. Several 'comprehensive' models have been proposed such as RADM (Chang, et al., 1987), STEM-II (Carmichael, et al., 1986), and CMAQ (Community Multi-scale Air Quality model, e.g., EPA website, 2003); the 'comprehensive' models include not only gas/aerosol phase chemistry but also aqueous phase chemistry in cloud/rain water in addition to the processes of advection, diffusion, wet deposition (mass transfer between aqueous and gas/aerosol phases), and dry deposition. The target of the development of the 'comprehensive' model will be that the model can correctly reproduce mass balance of various chemical species in the atmosphere with keeping adequate accuracy for calculated concentration distributions of chemical species. For the purpose, one of the important problems is a reliable wet deposition modeling, and here, we introduce two types of methods of 'cloud-resolving' and 'non-cloud-resolving' modeling for the wet deposition of pollutants. (author)

Solution chemistry of lanthanide complexes

International Nuclear Information System (INIS)

Brittain, H.G.

1979-01-01

Intermolecular energy transfer from Tb 3+ to Eu 3+ , luminescence intensity measurements, potentiometric titrations, differential absorption spectroscopy, and spectroscopic titrations were all used to study the binding of lanthanide ions by serine and threonine. At low pH (3.0 to 6.0) the complexes are mononuclear and ligand is only weakly bound. In the pH interval of 6.0 to 8.5 stronger interaction takes place between the ligand and the metal (with possible coordination of the undissociated hydroxyl group), and self-association of complexes becomes important. Above pH 8.5, base hydrolysis of the complexes leads to highly associated species in solution and shortly above this pH an insoluble precipitate is formed. It was found that energy could be transferred from Tb 3+ to Eu 3+ more efficiently among complexes prepared from racemic ligands than in complexes made from resolved ligand, but this stereoselectivity was only observed at pH values greater than 6.5 and in solutions having a 1:10 ratio of metal-to-ligand. No stereoselectivity was found in solutions having 1:5 ratios, and this observation was explained by the existence of 1:2 metal-ligand complexes existing in solutions having the higher ratio of metal-to-ligand (only 1:1 complexes are then found at lower ratios of metal-to-ligand). (author)

The chemistry of the actinide elements. Volume I

International Nuclear Information System (INIS)

Katz, J.J.; Seaborg, G.T.; Morss, L.R.

1986-01-01

The Chemistry of the Actinide Elements is a comprehensive, contemporary and authoritative exposition of the chemistry and related properties of the 5f series of elements: actinium, thorium, protactinium, uranium and the first eleven. This second edition has been completely restructured and rewritten to incorporate current research in all areas of actinide chemistry and chemical physics. The descriptions of each element include accounts of their history, separation, metallurgy, solid-state chemistry, solution chemistry, thermo-dynamics and kinetics. Additionally, separate chapters on spectroscopy, magnetochemistry, thermodynamics, solids, the metallic state, complex ions and organometallic compounds emphasize the comparative chemistry and unique properties of the actinide series of elements. Comprehensive lists of properties of all actinide compounds and ions in solution are given, and there are special sections on such topics as biochemistry, superconductivity, radioisotope safety, and waste management, as well as discussion of the transactinides and future elements

The slow birth of green chemistry

Energy Technology Data Exchange (ETDEWEB)

Amato, I.

1993-03-12

Mainstream chemistry is beginning to look at environmental chemistry as an important solution to environmental problems. This can include research into developing cleaner-burning liquid fuels, cleaning up oil spills, or developing better process methods which engender less pollution, as opposed to previous practices of detecting pollutants without preventing their release to begin with. This article discusses the progress of this chemistry discipline, describes some of the ongoing research, and describes the future for environmental chemistry. An impetus for future growth will be generational change, as young scientists in training are beginning to push faculities into creating programs for environmental chemistry.

Exploiting Locality in Quantum Computation for Quantum Chemistry.

Science.gov (United States)

McClean, Jarrod R; Babbush, Ryan; Love, Peter J; Aspuru-Guzik, Alán

2014-12-18

Accurate prediction of chemical and material properties from first-principles quantum chemistry is a challenging task on traditional computers. Recent developments in quantum computation offer a route toward highly accurate solutions with polynomial cost; however, this solution still carries a large overhead. In this Perspective, we aim to bring together known results about the locality of physical interactions from quantum chemistry with ideas from quantum computation. We show that the utilization of spatial locality combined with the Bravyi-Kitaev transformation offers an improvement in the scaling of known quantum algorithms for quantum chemistry and provides numerical examples to help illustrate this point. We combine these developments to improve the outlook for the future of quantum chemistry on quantum computers.

Results of an interactively coupled atmospheric chemistry – general circulation model: Comparison with observations

Directory of Open Access Journals (Sweden)

R. Hein

Full Text Available The coupled climate-chemistry model ECHAM4.L39(DLR/CHEM is presented which enables a simultaneous treatment of meteorology and atmospheric chemistry and their feedbacks. This is the first model which interactively combines a general circulation model with a chemical model, employing most of the important reactions and species necessary to describe the stratospheric and upper tropospheric ozone chemistry, and which is computationally fast enough to allow long-term integrations with currently available computer resources. This is possible as the model time-step used for the chemistry can be chosen as large as the integration time-step for the dynamics. Vertically the atmosphere is discretized by 39 levels from the surface up to the top layer which is centred at 10 hPa, with a relatively high vertical resolution of approximately 700 m near the extra-tropical tropopause. We present the results of a control simulation representing recent conditions (1990 and compare it to available observations. The focus is on investigations of stratospheric dynamics and chemistry relevant to describe the stratospheric ozone layer. ECHAM4.L39(DLR/CHEM reproduces main features of stratospheric dynamics in the arctic vortex region, including stratospheric warming events. This constitutes a major improvement compared to earlier model versions. However, apparent shortcomings in Antarctic circulation and temperatures persist. The seasonal and interannual variability of the ozone layer is simulated in accordance with observations. Activation and deactivation of chlorine in the polar stratospheric vortices and their inter-hemispheric differences are reproduced. Considering methane oxidation as part of the dynamic-chemistry feedback results in an improved representation of the spatial distribution of stratospheric water vapour concentrations. The current model constitutes a powerful tool to investigate, for instance, the combined direct and indirect effects of anthropogenic

Experimental and modeling studies of small molecule chemistry in expanding spherical flames

Science.gov (United States)

Santner, Jeffrey

Accurate models of flame chemistry are required in order to predict emissions and flame properties, such that clean, efficient engines can be designed more easily. There are three primary methods used to improve such combustion chemistry models - theoretical reaction rate calculations, elementary reaction rate experiments, and combustion system experiments. This work contributes to model improvement through the third method - measurements and analysis of the laminar burning velocity at constraining conditions. Modern combustion systems operate at high pressure with strong exhaust gas dilution in order to improve efficiency and reduce emissions. Additionally, flames under these conditions are sensitized to elementary reaction rates such that measurements constrain modeling efforts. Measurement conditions of the present work operate within this intersection between applications and fundamental science. Experiments utilize a new pressure-release, heated spherical combustion chamber with a variety of fuels (high hydrogen content fuels, formaldehyde (via 1,3,5-trioxane), and C2 fuels) at pressures from 0.5--25 atm, often with dilution by water vapor or carbon dioxide to flame temperatures below 2000 K. The constraining ability of these measurements depends on their uncertainty. Thus, the present work includes a novel analytical estimate of the effects of thermal radiative heat loss on burning velocity measurements in spherical flames. For 1,3,5-trioxane experiments, global measurements are sufficiently sensitive to elementary reaction rates that optimization techniques are employed to indirectly measure the reaction rates of HCO consumption. Besides the influence of flame chemistry on propagation, this work also explores the chemistry involved in production of nitric oxide, a harmful pollutant, within flames. We find significant differences among available chemistry models, both in mechanistic structure and quantitative reaction rates. There is a lack of well

Chemistry management system for nuclear power plants

International Nuclear Information System (INIS)

Nagasawa, Katsumi; Maeda, Katsuji

1998-01-01

Recently, the chemistry management in the nuclear power plants has been changing from the problem solution to the predictive diagnosis and maintenance. It is important to maintain the integrity of plant operation by an adequate chemistry control. For these reasons, many plant operation data and chemistry analysis data should be collected and treated effectively to evaluate chemistry condition of the nuclear power plants. When some indications of chemistry anomalies occur, quick and effective root cause evaluation and countermeasures should be required. The chemistry management system has been developed as to provide sophisticate chemistry management in the nuclear power plants. This paper introduces the concept and functions of the chemistry management system for the nuclear power plants. (author)

A coordination chemistry approach for modeling trace element adsorption

International Nuclear Information System (INIS)

Bourg, A.C.M.

1986-01-01

The traditional distribution coefficient, Kd, is highly dependent on the water chemistry and the surface properties of the geological system being studied and is therefore quite inappropriate for use in predictive models. Adsorption, one of the many processes included in Kd values, is described here using a coordination chemistry approach. The concept of adsorption of cationic trace elements by solid hydrous oxides can be applied to natural solids. The adsorption process is thus understood in terms of a classical complexation leading to the formation of surface (heterogeneous) ligands. Applications of this concept to some freshwater, estuarine and marine environments are discussed. (author)

Effects of feed solution chemistry on low pressure reverse osmosis filtration of cesium and strontium

Energy Technology Data Exchange (ETDEWEB)

Ding, Shiyuan, E-mail: dingshiyuan@bnu.edu.cn [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, No. 19, Xinjiekouwai Street, Haidian District, Beijing 100875 (China); Yang, Yu, E-mail: yangyu@bnu.edu.cn [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, No. 19, Xinjiekouwai Street, Haidian District, Beijing 100875 (China); Huang, Haiou, E-mail: huanghaiou@bnu.edu.cn [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, No. 19, Xinjiekouwai Street, Haidian District, Beijing 100875 (China); Liu, Hengchen, E-mail: 799599501@qq.com [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, No. 19, Xinjiekouwai Street, Haidian District, Beijing 100875 (China); Hou, Li-an, E-mail: houlian678@hotmail.com [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, No. 19, Xinjiekouwai Street, Haidian District, Beijing 100875 (China); Xi’an High-Tech Institute, No. 2, Tongxin Street, Baqiao District, Xi’an 710025 (China)

2015-08-30

Highlights: • A low pressure spiral wound RO membrane can reject Cs and Sr efficiently. • The rejection of Cs and Sr is dependent on feed pH and co-existing ions. • Donnan exclusion and electrostatic interaction govern the rejection of Cs and Sr. • The differences of filtration mechanism were influenced by the size of ions. • Sr could strengthen the irreversible membrane fouling resistance with HA. - Abstract: The objective of this study was to identify the removal mechanisms of radionuclides by reverse osmosis (RO) membranes under conditions relevant to full-scale water treatment. For this purpose, the effects of feed solution chemistry on the removal of Cs and Sr by a low pressure RO system was investigated by systematically varying membrane surface charge, ionic composition, and organic matter concentrations. The results showed that the effects of solution chemistry on the filtration of Cs and Sr were related to their hydrated ionic radius, resulting in the predominance of the Donnan’s effect and electrostatic interactions, respectively. Consequently, the rejection of Cs increased more pronouncedly than Sr with the increases of feed concentration. Due to the Donnan’s effect, different anions decreased the rejection of Cs to different extents in accordance to the order of anions’ radii as SO{sub 4}{sup 2−} > Cl{sup −} > NO{sub 3}{sup −} > F{sup −}. The variations in Sr rejection were influenced by the electrostatic interactions between Sr{sup 2+} and the membrane. In addition, humic acid (HA) lowered the rejection of Cs and caused significant membrane flux decline, but did not change the rejection of Sr. Sr also aggravated HA fouling of the membrane.

A Model of Titan-like Chemistry to Connect Experiments and Cassini Observations

Science.gov (United States)

Raymond, Alexander W.; Sciamma-O’Brien, Ella; Salama, Farid; Mazur, Eric

2018-02-01

A numerical model is presented for interpreting the chemical pathways that lead to the experimental mass spectra acquired in the Titan Haze Simulation (THS) laboratory experiments and for comparing the electron density and temperature of the THS plasma to observations made at Titan by the Cassini spacecraft. The THS plasma is a pulsed glow-discharge experiment designed to simulate the reaction of N2/CH4-dominated gas in Titan's upper atmosphere. The transient, one-dimensional model of THS chemistry tracks the evolution of more than 120 species in the direction of the plasma flow. As the minor species C2H2 and C2H4 are added to the N2/CH4-based mixture, the model correctly predicts the emergence of reaction products with up to five carbon atoms in relative abundances that agree well with measured mass spectra. Chemical growth in Titan's upper atmosphere transpires through ion–neutral and neutral–neutral chemistry, and the main reactions involving a series of known atmospheric species are retrieved from the calculation. The model indicates that the electron density and chemistry are steady during more than 99% of the 300 μs long discharge pulse. The model also suggests that the THS ionization fraction and electron temperature are comparable to those measured in Titan's upper atmosphere. These findings reaffirm that the THS plasma is a controlled analog environment for studying the first and intermediate steps of chemistry in Titan's upper atmosphere.

Influence of solution chemistry on the boron content in inorganic calcite grown in artificial seawater

Science.gov (United States)

Uchikawa, Joji; Harper, Dustin T.; Penman, Donald E.; Zachos, James C.; Zeebe, Richard E.

2017-12-01

The ratio of boron to calcium (B/Ca) in marine biogenic carbonates has been proposed as a proxy for properties of seawater carbonate chemistry. Applying this proxy to planktic foraminifera residing in the surface seawater largely in equilibrium with the atmosphere may provide a valuable handle on past atmospheric CO2 concentrations. However, precise controls on B/Ca in planktic foraminifera remain enigmatic because it has been shown to depend on multiple physicochemical seawater properties. To help establish a firm inorganic basis for interpreting the B/Ca records, we examined the effect of a suite of chemical parameters ([Ca2+], pH, [DIC], salinity and [PO43-]) on B/Ca in inorganic calcite precipitated in artificial seawater. These parameters were primarily varied individually while keeping all others constant, but we also tested the influence of pH and [DIC] at a constant calcite precipitation rate (R) by concurrent [Ca2+] adjustments. In the simple [Ca2+], pH and [DIC] experiments, both R and B/Ca increased with these parameters. In the pH-[Ca2+] and [DIC]-[Ca2+] experiments at constant R, on the other hand, B/Ca was invariant at different pH and decreased with [DIC], respectively. These patterns agree with the behavior of solution [BTotal/DIC] ratio such that, at a fixed [BTotal], it is independent of pH but decreases with [DIC]. Based on these results, R and [BTotal/DIC] ratio appear to be the primary controls on B/Ca in inorganic calcite, suggesting that both B(OH)4- and B(OH)3 are possibly involved in B incorporation. Moreover, B/Ca modestly increased with salinity and [PO43-]. Inorganic calcite precipitated at higher R and in the presence of oxyanions such as SO42- and PO43- in growth solutions often undergoes surface roughening due to formation of crystallographic defects, vacancies and, occasionally, amorphous/hydrous CaCO3. These non-lattice sites may provide additional space for B, particularly B(OH)3. Consequently, besides the macroscopic influence of

The impact of solution chemistry of electrolyte on the sorption of pentachlorophenol and phenanthrene by natural hematite nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Zeng, Fanfeng; He, Yan, E-mail: yhe2006@zju.edu.cn; Lian, Zhenghua; Xu, Jianming, E-mail: jmxu@zju.edu.cn

2014-01-01

Hematite nanoparticles (NPs) were studied as a sorbent for hydrophobic organic contaminants (OCs) under natural ambient conditions through specially designed contrasting solution chemistry of electrolyte. Ionizable pentachlorophenol (PCP) and non-ionizable phenanthrene (PHE) were selected as representative OCs. The sorption capacities of PCP and PHE were pH-dependent, and a larger amount of PCP was sorbed at pH values below its pK{sub a} (4.75). However, the PHE sorption capacity was higher at relatively high or low pHs (e.g. below 4.0 and above 10.0), possibly due to the larger available surface area of the hematite NPs, caused by the higher values of net charges and charge density. Changes in pH might thus affect the sorption of OCs by hematite NPs, through modification of the surface characteristics of the sorbent and the electronic properties of the sorbate molecules. The influence of different ionic strengths indicated that the amounts of PCP and PHE sorbed by hematite NPs decreased as a concentration function of different types of ions (e.g. Na{sup +}, K{sup +}, Mg{sup 2 +} and Ca{sup 2 +}), with the underlying mechanism possibly being due to four interactions i.e. hydrogen-bonding, competitive sorption by ions in the ambient solution, screening effects and aggregation effects. The results confirmed that the surface chemistry of hematite NPs, the chemical properties of PCP and PHE, and solution chemistry (e.g. pH and ionic strength) of the electrolyte all played an important role in PCP and PHE sorption by hematite NPs. By comparison of both sorption capacity and ecologic advantages, our results suggested that natural hematite NPs would be more competitive and efficient for PCP and PHE sorption than engineered NPs. This finding increases our knowledge regarding the environmental function of natural NPs (such as hematite NPs) for OC remediation through manipulating their interfacial behavior. - Highlights: •Hematite NPs was tested for PCP/PHE sorption under

Effects of lime and wood ash on soil-solution chemistry, soil chemistry and nutritional status of a pine stand in northern Germany

International Nuclear Information System (INIS)

Ludwig, Bernard; Rumpf, Sabine; Mindrup, Michael; Meiwes, Karl-Josef; Khanna, Partap K.

2002-01-01

Lime and wood ash may be useful to improve acidic forest soils. A field experiment was conducted in a pine stand on a sandy podzol at Fuhrberg, Germany, which involved an application of dolomitic lime (3 t/ha) with three replications or wood ash (4.8 t/ha) without replications on the forest floor. During the 2 yr study period, lime affected the soil solution composition only slightly. Ash had a marked effect on solution chemistry of the mineral soil at 10 cm and the pH values dropped temporarily from 3.7 to 3.1. Nineteen months after the treatments, exchangeable calcium in the organic layer and mineral soil increased by 222 (lime addition) or 411 kg/ha (ash addition) and exchangeable magnesium increased by 101 (lime addition) or 39 kg/ha (ash addition). After ash addition, no marked change in heavy metal content was found below 4 cm of the organic layer. In the ash treatment, the potassium concentration of the 1-yr-old pine needles increased from 5.6 to 5.9 g/kg. This study suggests that ash from untreated wood may be recommended for amelioration of forest soils

The Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP): Overview and Description of Models, Simulations and Climate Diagnostics

Science.gov (United States)

Lamarque, J.-F.; Shindell, D. T.; Naik, V.; Plummer, D.; Josse, B.; Righi, M.; Rumbold, S. T.; Schulz, M.; Skeie, R. B.; Strode, S.;

The Extrapolar SWIFT model (version 1.0): fast stratospheric ozone chemistry for global climate models

Science.gov (United States)

Kreyling, Daniel; Wohltmann, Ingo; Lehmann, Ralph; Rex, Markus

2018-03-01

The Extrapolar SWIFT model is a fast ozone chemistry scheme for interactive calculation of the extrapolar stratospheric ozone layer in coupled general circulation models (GCMs). In contrast to the widely used prescribed ozone, the SWIFT ozone layer interacts with the model dynamics and can respond to atmospheric variability or climatological trends.The Extrapolar SWIFT model employs a repro-modelling approach, in which algebraic functions are used to approximate the numerical output of a full stratospheric chemistry and transport model (ATLAS). The full model solves a coupled chemical differential equation system with 55 initial and boundary conditions (mixing ratio of various chemical species and atmospheric parameters). Hence the rate of change of ozone over 24 h is a function of 55 variables. Using covariances between these variables, we can find linear combinations in order to reduce the parameter space to the following nine basic variables: latitude, pressure altitude, temperature, overhead ozone column and the mixing ratio of ozone and of the ozone-depleting families (Cly, Bry, NOy and HOy). We will show that these nine variables are sufficient to characterize the rate of change of ozone. An automated procedure fits a polynomial function of fourth degree to the rate of change of ozone obtained from several simulations with the ATLAS model. One polynomial function is determined per month, which yields the rate of change of ozone over 24 h. A key aspect for the robustness of the Extrapolar SWIFT model is to include a wide range of stratospheric variability in the numerical output of the ATLAS model, also covering atmospheric states that will occur in a future climate (e.g. temperature and meridional circulation changes or reduction of stratospheric chlorine loading).For validation purposes, the Extrapolar SWIFT model has been integrated into the ATLAS model, replacing the full stratospheric chemistry scheme. Simulations with SWIFT in ATLAS have proven that the

Radiation chemistry of salicylic and methyl substituted salicylic acids: Models for the radiation chemistry of pharmaceutical compounds

International Nuclear Information System (INIS)

Ayatollahi, Shakiba; Kalnina, Daina; Song, Weihua; Turks, Maris; Cooper, William J.

2013-01-01

Salicylic acid and its derivatives are components of many medications and moieties found in numerous pharmaceutical compounds. They have been used as models for various pharmaceutical compounds in pharmacological studies, for the treatment of pharmaceuticals and personal care products (PPCPs), and, reactions with natural organic matter (NOM). In this study, the radiation chemistry of benzoic acid, salicylic acid and four methyl substituted salicylic acids (MSA) is reported. The absolute bimolecular reaction rate constants for hydroxyl radical reaction with benzoic and salicylic acids as well as 3-methyl-, 4-methyl-, 5-methyl-, and 6-methyl-salicylic acid were determined (5.86±0.54)×10 9 , (1.07±0.07)×10 10 , (7.48±0.17)×10 9 , (7.31±0.29)×10 9 , (5.47±0.25)×10 9 , (6.94±0.10)×10 9 (M −1 s −1 ), respectively. The hydrated electron reaction rate constants were measured (3.02±0.10)×10 9 , (8.98±0.27)×10 9 , (5.39±0.21)×10 9 , (4.33±0.17)×10 9 , (4.72±0.15)×10 9 , (1.42±0.02)×10 9 (M −1 s −1 ), respectively. The transient absorption spectra for the six model compounds were examined and their role as model compounds for the radiation chemistry of pharmaceuticals investigated. - Highlights: • Free radical chemistry of salicylic and 4 methyl salicylic acids is investigated. • The transient absorptions spectra for model compounds are measured. • Absolute bimolecular reaction rate constants for hydroxyl radical are determined. • Solvated electron reaction rate constants are calculated. • The use of salicylic acids as models for pharmaceuticals is explored

PWR secondary water chemistry guidelines

International Nuclear Information System (INIS)

Bell, M.J.; Blomgren, J.C.; Fackelmann, J.M.

1982-10-01

Steam generators in pressurized water reactor (PWR) nuclear power plants have experienced tubing degradation by a variety of corrosion-related mechanisms which depend directly on secondary water chemistry. As a result of this experience, the Steam Generator Owners Group and EPRI have sponsored a major program to provide solutions to PWR steam generator problems. This report, PWR Secondary Water Chemistry Guidelines, in addition to presenting justification for water chemistry control parameters, discusses available analytical methods, data management and surveillance, and the management philosophy required to successfully implement the guidelines

A simple one-step chemistry model for partially premixed hydrocarbon combustion

Energy Technology Data Exchange (ETDEWEB)

Fernandez-Tarrazo, Eduardo [Instituto Nacional de Tecnica Aeroespacial, Madrid (Spain); Sanchez, Antonio L. [Area de Mecanica de Fluidos, Universidad Carlos III de Madrid, Leganes 28911 (Spain); Linan, Amable [ETSI Aeronauticos, Pl. Cardenal Cisneros 3, Madrid 28040 (Spain); Williams, Forman A. [Department of Mechanical and Aerospace Engineering, University of California San Diego, La Jolla, CA 92093-0411 (United States)

2006-10-15

This work explores the applicability of one-step irreversible Arrhenius kinetics with unity reaction order to the numerical description of partially premixed hydrocarbon combustion. Computations of planar premixed flames are used in the selection of the three model parameters: the heat of reaction q, the activation temperature T{sub a}, and the preexponential factor B. It is seen that changes in q with equivalence ratio f need to be introduced in fuel-rich combustion to describe the effect of partial fuel oxidation on the amount of heat released, leading to a universal linear variation q(f) for f>1 for all hydrocarbons. The model also employs a variable activation temperature T{sub a}(f) to mimic changes in the underlying chemistry in rich and very lean flames. The resulting chemistry description is able to reproduce propagation velocities of diluted and undiluted flames accurately over the whole flammability limit. Furthermore, computations of methane-air counterflow diffusion flames are used to test the proposed chemistry under nonpremixed conditions. The model not only predicts the critical strain rate at extinction accurately but also gives near-extinction flames with oxygen leakage, thereby overcoming known predictive limitations of one-step Arrhenius kinetics. (author)

Solving vertical transport and chemistry in air pollution models

NARCIS (Netherlands)

Berkvens, P.J.F.; Bochev, M.A.; Krol, M.C.; Peters, W.; Verwer, J.G.; Chock, David P.; Carmichael, Gregory R.; Brick, Patricia

2002-01-01

For the time integration of stiff transport-chemistry problems from air pollution modelling, standard ODE solvers are not feasible due to the large number of species and the 3D nature. The popular alternative, standard operator splitting, introduces artificial transients for short-lived species.

Solving Vertical Transport and Chemistry in Air Pollution Models

NARCIS (Netherlands)

Berkvens, P.J.F.; Bochev, M.A.; Verwer, J.G.; Krol, M.C.; Peters, W.

For the time integration of stiff transport-chemistry problems from air pollution modelling, standard ODE solvers are not feasible due to the large number of species and the 3D nature. The popular alternative, standard operator splitting, introduces artificial transients for short-lived species.

Solution chemistry and separation of metal ions in leached solution

International Nuclear Information System (INIS)

Shibata, J.

1991-01-01

The method to presume a dissolved state of metal ions in an aqueous solution and the technology to separate and concentrate metal ions in a leached solution are described in this paper. It is very important for the separation of metal ions to know the dissolved state of metal ions. If we know the composition of an aqueous solution and the stability constants of metal-ligand complexes, we can calculate and estimate the concentration of each species in the solution. Then, we can decide the policy to separate and concentrate metal ions. There are several methods for separation and purification; hydroxide precipitation method, sulfide precipitation method, solvent extraction method and ion exchange resin method. Solvent extraction has been used in purification processes of copper refinery, uranium refinery, platinum metal refinery and rare earth metal refinery. Fundamental process of solvent extraction, a kind of commercial extractants, a way of determining a suitable extractant and an equipment are discussed. Finally, it will be emphasized how the separation of rare earths is improved in solvent extraction. (author) 21 figs., 8 tabs., 8 refs

Pretreatment of lignocellulosic biomass using Fenton chemistry

Science.gov (United States)

Pretreatment is a necessary step in “biomass to biofuel conversion” due to the recalcitrant nature of lignocellulosic biomass. White-rot fungi utilize peroxidases and hydrogen peroxide (in vivo Fenton chemistry) to degrade lignin. In an attempt to mimic this process, solution phase Fenton chemistry ...

Online coupled regional meteorology chemistry models in Europe : Current status and prospects

NARCIS (Netherlands)

Baklanov, A.; Schlünzen, K.; Suppan, P.; Baldasano, J.; Brunner, D.; Aksoyoglu, S.; Carmichael, G.; Douros, J.; Flemming, J.; Forkel, R.; Galmarini, S.; Gauss, M.; Grell, G.; Hirtl, M.; Joffre, S.; Jorba, O.; Kaas, E.; Kaasik, M.; Kallos, G.; Kong, X.; Korsholm, U.; Kurganskiy, A.; Kushta, J.; Lohmann, U.; Mahura, A.; Manders-Groot, A.; Maurizi, A.; Moussiopoulos, N.; Rao, S.T.; Savage, N.; Seigneur, C.; Sokhi, R.S.; Solazzo, E.; Solomos, S.; Sørensen, B.; Tsegas, G.; Vignati, E.; Vogel, B.; Zhang, Y.

2014-01-01

Online coupled mesoscale meteorology atmospheric chemistry models have undergone a rapid evolution in recent years. Although mainly developed by the air quality modelling community, these models are also of interest for numerical weather prediction and regional climate modelling as they can consider

he Impact of Primary Marine Aerosol on Atmospheric Chemistry, Radiation and Climate: A CCSM Model Development Study

Energy Technology Data Exchange (ETDEWEB)

Keene, William C. [University of Virginia; Long, Michael S. [University of Virginia

2013-05-20

This project examined the potential large-scale influence of marine aerosol cycling on atmospheric chemistry, physics and radiative transfer. Measurements indicate that the size-dependent generation of marine aerosols by wind waves at the ocean surface and the subsequent production and cycling of halogen-radicals are important but poorly constrained processes that influence climate regionally and globally. A reliable capacity to examine the role of marine aerosol in the global-scale atmospheric system requires that the important size-resolved chemical processes be treated explicitly. But the treatment of multiphase chemistry across the breadth of chemical scenarios encountered throughout the atmosphere is sensitive to the initial conditions and the precision of the solution method. This study examined this sensitivity, constrained it using high-resolution laboratory and field measurements, and deployed it in a coupled chemical-microphysical 3-D atmosphere model. First, laboratory measurements of fresh, unreacted marine aerosol were used to formulate a sea-state based marine aerosol source parameterization that captured the initial organic, inorganic, and physical conditions of the aerosol population. Second, a multiphase chemical mechanism, solved using the Max Planck Institute for Chemistry's MECCA (Module Efficiently Calculating the Chemistry of the Atmosphere) system, was benchmarked across a broad set of observed chemical and physical conditions in the marine atmosphere. Using these results, the mechanism was systematically reduced to maximize computational speed. Finally, the mechanism was coupled to the 3-mode modal aerosol version of the NCAR Community Atmosphere Model (CAM v3.6.33). Decadal-scale simulations with CAM v.3.6.33, were run both with and without reactive-halogen chemistry and with and without explicit treatment of particulate organic carbon in the marine aerosol source function. Simulated results were interpreted (1) to evaluate influences

Effects of wood ash on soil solution and chemistry of leaves in a beech stand

International Nuclear Information System (INIS)

Tothova, Slavka

2005-01-01

The short-term effects of wood ash fertilization on chemistry of soil solution and leaves were investigated in 4-year-old beech stand (Fagus sylvatica L.) on dystric cambisol in Central Spis. Four plots - the control plot and three plots with different ash treatments (different dose, date and method of application) were established. Plate lysimeters were installed under the upper layer of soil in depth 2 cm and 20 cm on the control plot and plot P1 with addition of wood ash 5 t/ha on the whole surface. Soil solution was collected in May - October 2002 every two weeks. Composite samples, which represent a one - month period, were analysed for pH, K, Ca, Mg, and NO 3 - . The leaves were collected 4 or 10 months after the treatment and analysed on Ca, K, Mg, P, S, N and heavy metals Cd, Pb, Cr and Hg. In the ash treatment the content of macronutrient increased (mainly K, Ca). Addition of ash did not increase of the content heavy metal in leaves

Tropospheric jet response to Antarctic ozone depletion: An update with Chemistry-Climate Model Initiative (CCMI) models

Science.gov (United States)

Son, Seok-Woo; Han, Bo-Reum; Garfinkel, Chaim I.; Kim, Seo-Yeon; Park, Rokjin; Abraham, N. Luke; Akiyoshi, Hideharu; Archibald, Alexander T.; Butchart, N.; Chipperfield, Martyn P.; Dameris, Martin; Deushi, Makoto; Dhomse, Sandip S.; Hardiman, Steven C.; Jöckel, Patrick; Kinnison, Douglas; Michou, Martine; Morgenstern, Olaf; O’Connor, Fiona M.; Oman, Luke D.; Plummer, David A.; Pozzer, Andrea; Revell, Laura E.; Rozanov, Eugene; Stenke, Andrea; Stone, Kane; Tilmes, Simone; Yamashita, Yousuke; Zeng, Guang

2018-05-01

The Southern Hemisphere (SH) zonal-mean circulation change in response to Antarctic ozone depletion is re-visited by examining a set of the latest model simulations archived for the Chemistry-Climate Model Initiative (CCMI) project. All models reasonably well reproduce Antarctic ozone depletion in the late 20th century. The related SH-summer circulation changes, such as a poleward intensification of westerly jet and a poleward expansion of the Hadley cell, are also well captured. All experiments exhibit quantitatively the same multi-model mean trend, irrespective of whether the ocean is coupled or prescribed. Results are also quantitatively similar to those derived from the Coupled Model Intercomparison Project phase 5 (CMIP5) high-top model simulations in which the stratospheric ozone is mostly prescribed with monthly- and zonally-averaged values. These results suggest that the ozone-hole-induced SH-summer circulation changes are robust across the models irrespective of the specific chemistry-atmosphere-ocean coupling.

Compacton solutions and multiple compacton solutions for a continuum Toda lattice model

International Nuclear Information System (INIS)

Fan Xinghua; Tian Lixin

2006-01-01

Some special solutions of the Toda lattice model with a transversal degree of freedom are obtained. With the aid of Mathematica and Wu elimination method, more explicit solitary wave solutions, including compacton solutions, multiple compacton solutions, peakon solutions, as well as periodic solutions are found in this paper

Controlling Chemistry in Dynamic Nanoscale Systems

DEFF Research Database (Denmark)

Jesorka, Aldo; Lizana, Ludvig; Konkoli, Zoran

2011-01-01

Spatial organization and shape dynamics are inherent properties of biological cells and cell interiors. There are strong indications that these features are important for the in vivo control of reaction parameters in biochemical transformations. Nanofluidic model devices founded on surfactant...... of the concept. Controlled release of chol-DNA molecules from SU-8 surfaces gives the possibility to dynamically change surface and/or solution properties in micro and nanoreactor applications, opening access to stable 2D chemistry on surface-based devices with potential for easy interfacing with conventional...

How does Interactive Chemistry Influence the Representation of Stratosphere-Troposphere Coupling in a Climate Model?

Science.gov (United States)

Haase, S.; Matthes, K. B.

2017-12-01

Changes in stratospheric ozone can trigger tropospheric circulation changes. In the Southern hemisphere (SH), the observed shift of the Southern Annular Mode was attributed to the observed trend in lower stratospheric ozone. In the Northern Hemisphere (NH), a recent study showed that extremely low stratospheric ozone conditions during spring produce robust anomalies in the troposphere (zonal wind, temperature and precipitation). This could only be reproduced in a coupled chemistry climate model indicating that chemical-dynamical feedbacks are also important on the NH. To further investigate the importance of interactive chemistry for surface climate, we conducted a set of experiments using NCAR's Community Earth System Model (CESM1) with the Whole Atmosphere Community Climate Model (WACCM) as the atmosphere component. WACCM contains a fully interactive stratospheric chemistry module in its standard configuration. It also allows for an alternative configuration, referred to as SC-WACCM, in which the chemistry (O3, NO, O, O2, CO2 and chemical and shortwave heating rates) is specified as a 2D field in the radiation code. A comparison of the interactive vs. the specified chemistry version enables us to evaluate the relative importance of interactive chemistry by systematically inhibiting the feedbacks between chemistry and dynamics. To diminish the effect of temporal interpolation when prescribing ozone, we use daily resolved zonal mean ozone fields for the specified chemistry run. Here, we investigate the differences in stratosphere-troposphere coupling between the interactive and specified chemistry simulations for the mainly chemically driven SH as well as for the mainly dynamically driven NH. We will especially consider years that are characterized by extremely low stratospheric ozone on the one hand and by large dynamical disturbances, i.e. Sudden Stratospheric Warmings, on the other hand.

Effects of '"Environmental Chemistry" Elective Course via Technology-Embedded Scientific Inquiry Model on Some Variables

Science.gov (United States)

Çalik, Muammer; Özsevgeç, Tuncay; Ebenezer, Jazlin; Artun, Hüseyin; Küçük, Zeynel

2014-01-01

The purpose of this study is to examine the effects of "environmental chemistry" elective course via Technology-Embedded Scientific Inquiry (TESI) model on senior science student teachers' (SSSTs) conceptions of environmental chemistry concepts/issues, attitudes toward chemistry, and technological pedagogical content knowledge…

The chemistry-climate model ECHAM6.3-HAM2.3-MOZ1.0

Science.gov (United States)

Schultz, Martin G.; Stadtler, Scarlet; Schröder, Sabine; Taraborrelli, Domenico; Franco, Bruno; Krefting, Jonathan; Henrot, Alexandra; Ferrachat, Sylvaine; Lohmann, Ulrike; Neubauer, David; Siegenthaler-Le Drian, Colombe; Wahl, Sebastian; Kokkola, Harri; Kühn, Thomas; Rast, Sebastian; Schmidt, Hauke; Stier, Philip; Kinnison, Doug; Tyndall, Geoffrey S.; Orlando, John J.; Wespes, Catherine

2018-05-01

The chemistry-climate model ECHAM-HAMMOZ contains a detailed representation of tropospheric and stratospheric reactive chemistry and state-of-the-art parameterizations of aerosols using either a modal scheme (M7) or a bin scheme (SALSA). This article describes and evaluates the model version ECHAM6.3-HAM2.3-MOZ1.0 with a focus on the tropospheric gas-phase chemistry. A 10-year model simulation was performed to test the stability of the model and provide data for its evaluation. The comparison to observations concentrates on the year 2008 and includes total column observations of ozone and CO from IASI and OMI, Aura MLS observations of temperature, HNO3, ClO, and O3 for the evaluation of polar stratospheric processes, an ozonesonde climatology, surface ozone observations from the TOAR database, and surface CO data from the Global Atmosphere Watch network. Global budgets of ozone, OH, NOx, aerosols, clouds, and radiation are analyzed and compared to the literature. ECHAM-HAMMOZ performs well in many aspects. However, in the base simulation, lightning NOx emissions are very low, and the impact of the heterogeneous reaction of HNO3 on dust and sea salt aerosol is too strong. Sensitivity simulations with increased lightning NOx or modified heterogeneous chemistry deteriorate the comparison with observations and yield excessively large ozone budget terms and too much OH. We hypothesize that this is an impact of potential issues with tropical convection in the ECHAM model.

Radiation chemistry and the environment

International Nuclear Information System (INIS)

Getoff, F.

1998-01-01

The rather strong and many-sided pollution of the environment (atmosphere, water resources, soil) as a consequence of human activities is summarized. The solution of the arised problems by application of radiation chemistry methods and the utilization of modern environmentally ''clean'' and economical technologies, founded on electron beam processing, are mentioned. Some basic environmental problems and their solution are briefly discussed: i) Removal of CO 2 from flue gases and its radiation induced utilization. ii) Principals for degradation of aqueous pollutants by electron beam processing in the presence of ozone (synergistic effect). The radiation chemistry as a modern and manifold discipline with very broad applications can also essentially contribute in the conservation of the environment

Radiation chemistry and the environment

International Nuclear Information System (INIS)

Getoff, Nikola

1999-01-01

The rather strong and many-sided pollution of the environment (atmosphere, water resources, soil) as a consequence of human activity is summarized. The solution of the arised problems by application of radiation chemistry methods and the utilization of modern environmentally 'clean' and economical technologies, founded on electron beam processing, are mentioned. Some basic environmental problems and their solution are briefly discussed. (i) Removal of CO 2 from flue gases and its radiation induced utilization. (ii) Principals for degradation of aqueous pollutants by electron beam processing in the presence of ozone (synergistic effect). The radiation chemistry as a modern and manifold discipline with very broad applications can also essentially contribute in the conservation of the environment

Vortex solutions in a Witten-type model

International Nuclear Information System (INIS)

Itaya, Satoru; Sawado, Nobuyuki; Suzuki, Michitaka

2014-01-01

Straight line vortex solutions in a Witten's superconducting string model are studied. The model has many parameters and this is the main reason of the complexity. We argue the precise conditions of the parameters for finding the solutions of the model. We obtain the rotationally symmetric solutions for the winding numbers m = 1 - 4 with/without the gauge field. For the higher winding numbers, an energy minimization algorithm is used to investigate non-rotational solutions

Chemistry of Protostellar Envelopes and Disks

Science.gov (United States)

Flores Rivera, Lizxandra; Terebey, Susan; Willacy, Karen

2018-06-01

Molecule formation is dynamic during the protostar collapse phase, driven by changes in temperature, density, and UV radiation as gas and dust flows from the envelope onto the forming protoplanetary disk. In this work, we compare physical models based on two different collapse solutions. We modeled the chemistry (created by Karen Willacy) for C18O to see how its abundance changes over time using as primary input parameters the temperature and density profile that were produced by the dust Radiative Transfer (MCRT) model called HOCHUNK3D from Whitney (2003). Given this model, we produce synthetic line emission maps from L1527 IRS to simulate the Class 0/I protostar L1527 IRS using RADMC3D code and compare them with previous observations from ALMA. High concentrations of gas phase molecules of C18O are found within the 20 AU in areas in the envelope that are close to the surface of the disk. In the outermost part of the disk surface, the C18O freezes out beyond 400 AU, showing a much reduced abundance where the temperature profile drops down below 25 K. In cold regions, the radiation field plays an important role in the chemistry.

A Model for Nitrogen Chemistry in Oxy-Fuel Combustion of Pulverized Coal

DEFF Research Database (Denmark)

Hashemi, Hamid; Hansen, Stine; Toftegaard, Maja Bøg

2011-01-01

, heating and devolatilization of particles, and gas–solid reactions. The model is validated by comparison with entrained flow reactor results from the present work and from the literature on pulverized coal combustion in O2/CO2 and air, covering the effects of fuel, mixing conditions, temperature......In this work, a model for the nitrogen chemistry in the oxy-fuel combustion of pulverized coal has been developed. The model is a chemical reaction engineering type of model with a detailed reaction mechanism for the gas-phase chemistry, together with a simplified description of the mixing of flows......, stoichiometry, and inlet NO level. In general, the model provides a satisfactory description of NO formation in air and oxy-fuel combustion of coal, but under some conditions, it underestimates the impact on NO of replacing N2 with CO2. According to the model, differences in the NO yield between the oxy...

An algorithm for variational data assimilation of contact concentration measurements for atmospheric chemistry models

Science.gov (United States)

Penenko, Alexey; Penenko, Vladimir

2014-05-01

Contact concentration measurement data assimilation problem is considered for convection-diffusion-reaction models originating from the atmospheric chemistry study. High dimensionality of models imposes strict requirements on the computational efficiency of the algorithms. Data assimilation is carried out within the variation approach on a single time step of the approximated model. A control function is introduced into the source term of the model to provide flexibility for data assimilation. This function is evaluated as the minimum of the target functional that connects its norm to a misfit between measured and model-simulated data. In the case mathematical model acts as a natural Tikhonov regularizer for the ill-posed measurement data inversion problem. This provides flow-dependent and physically-plausible structure of the resulting analysis and reduces a need to calculate model error covariance matrices that are sought within conventional approach to data assimilation. The advantage comes at the cost of the adjoint problem solution. This issue is solved within the frameworks of splitting-based realization of the basic convection-diffusion-reaction model. The model is split with respect to physical processes and spatial variables. A contact measurement data is assimilated on each one-dimensional convection-diffusion splitting stage. In this case a computationally-efficient direct scheme for both direct and adjoint problem solution can be constructed based on the matrix sweep method. Data assimilation (or regularization) parameter that regulates ratio between model and data in the resulting analysis is obtained with Morozov discrepancy principle. For the proper performance the algorithm takes measurement noise estimation. In the case of Gaussian errors the probability that the used Chi-squared-based estimate is the upper one acts as the assimilation parameter. A solution obtained can be used as the initial guess for data assimilation algorithms that assimilate

Chemistry and Transport In a Multi-Dimensional Model

Science.gov (United States)

Yung, Yuk L.; Allen, M.; Zurek, R. W.; Salawitch, R. J.

2002-01-01

The focus of the work funded under this proposal is the exchange between the stratosphere and the troposphere, and between the troposphere and the blaspheme. These two interfaces represent the frontiers of atmospheric chemistry. It is the combination of exchange processes at both interfaces that ultimately controls how the blaspheme (including human activities) affects the ozone layer. The modeling work was motivated by and attempts to integrate information obtained by aircraft, spacecraft, shuttle and oceanic measurements. The model development and research activities accomplished in the past three years provide a technical and intellectual basis for the research in this group. The innovative part of our research program is related to the IAV of ozone and the hydrological cycle. Other related but independently supported work include the study of isotopic fractionation of atmospheric species, e.g., N2O and CO2. Our theory suggests that we now have the ability to probe the middle atmosphere at a level of sensitivity where subtle details such as the isotopic composition of simple molecules can yield measurable systematic effects. This creates the possibility for probing the chemistry and dynamics of the middle atmosphere using all of the N2O and CO2 isotopologues. In the following we will briefly describe the model development and review the highlights of recent accomplishments.

Effects of Solution Chemistry on Nano-Bubbles Transport in Saturated Porous Media

Science.gov (United States)

Hamamoto, S.; Takemura, T.; Suzuki, K.; Nihei, N.; Nishimura, T.

2017-12-01

Nano-bubbles (NBs) have a considerable potential for the remediation of soil and groundwater contaminated by organic compounds, especially when used in conjunction with bioremediation technologies. Understanding the transport mechanisms of NBs in soils is essential to optimize NB-based remediation techniques. In this study, one-dimensional column transport experiments using glass beads with 0.1 mm size were conducted, where NBs created by oxygen gas at different pH and ionic strength were injected to the column at the constant flow rate. The NBs concentration in the effluent was quantified using a resonant mass measurement technique. Effects of solution chemistry of the NBs water on NB transport in the porous media were investigated. The results showed that attachment of NBs was enhanced under higher ionic strength and lower pH conditions, caused by the reduced repulsive force between NBs and glass beads. In addition, bubble size distributions in the effluents showed that relatively larger NBs were retained in the column. This trend was more significant at lower pH condition.

An advanced modeling study on the impacts and atmospheric implications of multiphase dimethyl sulfide chemistry

Science.gov (United States)

Hoffmann, Erik Hans; Tilgner, Andreas; Schrödner, Roland; Bräuer, Peter; Wolke, Ralf; Herrmann, Hartmut

2016-01-01

Oceans dominate emissions of dimethyl sulfide (DMS), the major natural sulfur source. DMS is important for the formation of non-sea salt sulfate (nss-SO42−) aerosols and secondary particulate matter over oceans and thus, significantly influence global climate. The mechanism of DMS oxidation has accordingly been investigated in several different model studies in the past. However, these studies had restricted oxidation mechanisms that mostly underrepresented important aqueous-phase chemical processes. These neglected but highly effective processes strongly impact direct product yields of DMS oxidation, thereby affecting the climatic influence of aerosols. To address these shortfalls, an extensive multiphase DMS chemistry mechanism, the Chemical Aqueous Phase Radical Mechanism DMS Module 1.0, was developed and used in detailed model investigations of multiphase DMS chemistry in the marine boundary layer. The performed model studies confirmed the importance of aqueous-phase chemistry for the fate of DMS and its oxidation products. Aqueous-phase processes significantly reduce the yield of sulfur dioxide and increase that of methyl sulfonic acid (MSA), which is needed to close the gap between modeled and measured MSA concentrations. Finally, the simulations imply that multiphase DMS oxidation produces equal amounts of MSA and sulfate, a result that has significant implications for nss-SO42− aerosol formation, cloud condensation nuclei concentration, and cloud albedo over oceans. Our findings show the deficiencies of parameterizations currently used in higher-scale models, which only treat gas-phase chemistry. Overall, this study shows that treatment of DMS chemistry in both gas and aqueous phases is essential to improve the accuracy of model predictions. PMID:27688763

Self-assembly in casting solutions of block copolymer membranes

KAUST Repository

Marques, Debora S.; Vainio, Ulla; Moreno Chaparro, Nicolas; Calo, Victor M.; Bezahd, Ali Reza; Pitera, Jed W.; Peinemann, Klaus; Nunes, Suzana Pereira

2013-01-01

Membranes with exceptional pore regularity and high porosity were obtained from block copolymer solutions. We demonstrate by small-angle X-ray scattering that the order which gives rise to the pore morphology is already incipient in the casting solution. Hexagonal order was confirmed in PS-b-P4VP 175k-b-65k solutions in DMF/THF/dioxane with concentrations as high as 24 wt%, while lamellar structures were obtained in more concentrated solutions in DMF or DMF/dioxane. The change in order has been understood with the support of dissipative particle dynamic modeling. © 2013 The Royal Society of Chemistry.

A general method for the inclusion of radiation chemistry in astrochemical models.

Science.gov (United States)

Shingledecker, Christopher N; Herbst, Eric

2018-02-21

In this paper, we propose a general formalism that allows for the estimation of radiolysis decomposition pathways and rate coefficients suitable for use in astrochemical models, with a focus on solid phase chemistry. Such a theory can help increase the connection between laboratory astrophysics experiments and astrochemical models by providing a means for modelers to incorporate radiation chemistry into chemical networks. The general method proposed here is targeted particularly at the majority of species now included in chemical networks for which little radiochemical data exist; however, the method can also be used as a starting point for considering better studied species. We here apply our theory to the irradiation of H 2 O ice and compare the results with previous experimental data.

Polish contribution to radiation chemistry

International Nuclear Information System (INIS)

Kroh, J.

1989-01-01

This article outlines the history of radiation chemistry research in Poland from 1899 to the present day, with particular reference to radiolysis studies of aqueous solutions of radioactive compounds. (UK)

Sketching the Invisible to Predict the Visible: From Drawing to Modeling in Chemistry.

Science.gov (United States)

Cooper, Melanie M; Stieff, Mike; DeSutter, Dane

2017-10-01

Sketching as a scientific practice goes beyond the simple act of inscribing diagrams onto paper. Scientists produce a wide range of representations through sketching, as it is tightly coupled to model-based reasoning. Chemists in particular make extensive use of sketches to reason about chemical phenomena and to communicate their ideas. However, the chemical sciences have a unique problem in that chemists deal with the unseen world of the atomic-molecular level. Using sketches, chemists strive to develop causal mechanisms that emerge from the structure and behavior of molecular-level entities, to explain observations of the macroscopic visible world. Interpreting these representations and constructing sketches of molecular-level processes is a crucial component of student learning in the modern chemistry classroom. Sketches also serve as an important component of assessment in the chemistry classroom as student sketches give insight into developing mental models, which allows instructors to observe how students are thinking about a process. In this paper we discuss how sketching can be used to promote such model-based reasoning in chemistry and discuss two case studies of curricular projects, CLUE and The Connected Chemistry Curriculum, that have demonstrated a benefit of this approach. We show how sketching activities can be centrally integrated into classroom norms to promote model-based reasoning both with and without component visualizations. Importantly, each of these projects deploys sketching in support of other types of inquiry activities, such as making predictions or depicting models to support a claim; sketching is not an isolated activity but is used as a tool to support model-based reasoning in the discipline. Copyright © 2017 Cognitive Science Society, Inc.

Optimisation-Based Solution Methods for Set Partitioning Models

DEFF Research Database (Denmark)

Rasmussen, Matias Sevel

The scheduling of crew, i.e. the construction of work schedules for crew members, is often not a trivial task, but a complex puzzle. The task is complicated by rules, restrictions, and preferences. Therefore, manual solutions as well as solutions from standard software packages are not always su......_cient with respect to solution quality and solution time. Enhancement of the overall solution quality as well as the solution time can be of vital importance to many organisations. The _elds of operations research and mathematical optimisation deal with mathematical modelling of di_cult scheduling problems (among...... other topics). The _elds also deal with the development of sophisticated solution methods for these mathematical models. This thesis describes the set partitioning model which has been widely used for modelling crew scheduling problems. Integer properties for the set partitioning model are shown...

Promoting sustainability through green chemistry

Energy Technology Data Exchange (ETDEWEB)

Kirchhoff, Mary M. [American Chemical Society, 1155 Sixteenth Street, NW, Washington, DC 20036 (United States)

2005-06-15

Green chemistry is an important tool in achieving sustainability. The implementation of green chemistry, the design of chemical products and processes that reduce or eliminate the use and generation of hazardous substances, is essential if the expanding global population is to enjoy an increased standard of living without having a negative impact on the health of the planet. Cleaner technologies will allow the chemical enterprise to provide society with the goods and services on which it depends in an environmentally responsible manner. Green chemistry provides solutions to such global challenges as climate change, sustainable agriculture, energy, toxics in the environment, and the depletion of natural resources. A collaborative effort by industry, academia, and government is needed to promote the adoption of the green chemistry technologies necessary to achieve a sustainable society.

Prediction of the effects of soil-based countermeasures on soil solution chemistry of soils contaminated with radiocesium using the hydrogeochemical code PHREEQC.

Science.gov (United States)

Hormann, Volker; Kirchner, Gerald

2002-04-22

For agriculturally used areas, which are contaminated by the debris from a nuclear accident, the use of chemical amendmends (e.g. potassium chloride and lime) is among the most common soil-based countermeasures. These countermeasures are intended to reduce the plant uptake of radionuclides (mainly 137Cs and 90Sr) by competitive inhibition by chemically similar ions. So far, the impacts of countermeasures on soil solution composition - and thus, their effectiveness - have almost exclusively been established experimentally, since they depend on mineral composition and chemical characteristics of the soil affected. In this study, which focuses on caesium contamination, the well-established code PHREEQC was used as a geochemical model to calculate the changes in the ionic compositions of soil solutions, which result from the application of potassium or ammonium in batch equilibrium experiments. The simple ion exchange model used by PHREEQC was improved by taking into account selective sorption of Cs+, NH4+ and K+ by clay minerals. Calculations were performed with three different initial soil solution compositions, corresponding to particular soil types (loam, sand, peat). For loamy and sandy soils, our calculational results agree well with experimental data reported by Nisbet (Effectiveness of soil-based countermeasures six months and one year after contamination of five diverse soil types with caesium-134 and strontium-90. Contract Report NRPB-M546, National Radiation Protection Board, Chilton, 1995.). For peat, discrepancies were found indicating that for organic soils a reliable set of exchange constants of the relevant cations still has to be determined experimentally. For cesium, however, these discrepancies almost disappeared if selective sites were assumed to be inaccessible. Additionally, results of sensitivity analyses are presented by which the influence of the main soil parameters on Cs+ concentrations in solution after soil treatment has been systematically

On the comparison of numerical methods for the integration of kinetic equations in atmospheric chemistry and transport models

Science.gov (United States)

Saylor, Rick D.; Ford, Gregory D.

The integration of systems of ordinary differential equations (ODEs) that arise in atmospheric photochemistry is of significant concern to tropospheric and stratospheric chemistry modelers. As a consequence of the stiff nature of these ODE systems, their solution requires a large fraction of the total computational effort in three-dimensional chemical model simulations. Several integration techniques have been proposed and utilized over the years in an attempt to provide computationally efficient, yet accurate, solutions to chemical kinetics ODES. In this work, we present a comparison of some of these techniques and argue that valid comparisons of ODE solvers must take into account the trade-off between solution accuracy and computational efficiency. Misleading comparison results can be obtained by neglecting the fact that any ODE solution method can be made faster or slower by manipulation of the appropriate error tolerances or time steps. Comparisons among ODE solution techniques should therefore attempt to identify which technique can provide the most accurate solution with the least computational effort over the entire range of behavior of each technique. We present here a procedure by which ODE solver comparisons can achieve this goal. Using this methodology, we compare a variety of integration techniques, including methods proposed by Hesstvedt et al. (1978, Int. J. Chem. Kinet.10, 971-994), Gong and Cho (1993, Atmospheric Environment27A, 2147-2160), Young and Boris (1977, J. phys. Chem.81, 2424-2427) and Hindmarsh (1983, In Scientific Computing (edited by Stepleman R. S. et al.), pp. 55-64. North-Holland, Amsterdam). We find that Gear-type solvers such as the Livermore Solver for ordinary differential equations (LSODE) and the sparse-matrix version of LSODE (LSODES) provide the most accurate solution of our test problems with the least computational effort.

Modelling the urban air quality in Hamburg with the new city-scale chemistry transport model CityChem

Science.gov (United States)

Karl, Matthias; Ramacher, Martin; Aulinger, Armin; Matthias, Volker; Quante, Markus

2017-04-01

Air quality modelling plays an important role by providing guidelines for efficient air pollution abatement measures. Currently, most urban dispersion models treat air pollutants as passive tracer substances or use highly simplified chemistry when simulating air pollutant concentrations on the city-scale. The newly developed urban chemistry-transport model CityChem has the capability of modelling the photochemical transformation of multiple pollutants along with atmospheric diffusion to produce pollutant concentration fields for the entire city on a horizontal resolution of 100 m or even finer and a vertical resolution of 24 layers up to 4000 m height. CityChem is based on the Eulerian urban dispersion model EPISODE of the Norwegian Institute for Air Research (NILU). CityChem treats the complex photochemistry in cities using detailed EMEP chemistry on an Eulerian 3-D grid, while using simple photo-stationary equilibrium on a much higher resolution grid (receptor grid), i.e. close to industrial point sources and traffic sources. The CityChem model takes into account that long-range transport contributes to urban pollutant concentrations. This is done by using 3-D boundary concentrations for the city domain derived from chemistry-transport simulations with the regional air quality model CMAQ. For the study of the air quality in Hamburg, CityChem was set-up with a main grid of 30×30 grid cells of 1×1 km2 each and a receptor grid of 300×300 grid cells of 100×100 m2. The CityChem model was driven with meteorological data generated by the prognostic meteorology component of the Australian chemistry-transport model TAPM. Bottom-up inventories of emissions from traffic, industry, households were based on data of the municipality of Hamburg. Shipping emissions for the port of Hamburg were taken from the Clean North Sea Shipping project. Episodes with elevated ozone (O3) were of specific interest for this study, as these are associated with exceedances of the World

Application of solution-mineral equilibrium chemistry to solution mining of uranium ores

International Nuclear Information System (INIS)

Riese, A.C.; Popp, C.J.

1979-01-01

The tests described were undertaken to determine the extent to leach solution-rock interactions with uranium-bearing ore obtained from the Mariano Lake mine. Leach solutions of an acidic (H/sub 2/O/sub 4/-sulfuric acid) and basic (NaHCO/sub 3/-sodium bicarbonate) nature were tested, in addition to a leach solution containing potassium chloride and sulfuric acid (KCl/H/sub 2/SO/sub 4/). The latter solution was chosen in an attempt to equilibrate the aqueous phase with the rock-forming silicate minerals and minimize adverse effects such as clay formation, porosity loss, and lixiviant loss. 29 refs

A computer model for one-dimensional mass and energy transport in and around chemically reacting particles, including complex gas-phase chemistry, multicomponent molecular diffusion, surface evaporation, and heterogeneous reaction

Science.gov (United States)

Cho, S. Y.; Yetter, R. A.; Dryer, F. L.

1992-01-01

Various chemically reacting flow problems highlighting chemical and physical fundamentals rather than flow geometry are presently investigated by means of a comprehensive mathematical model that incorporates multicomponent molecular diffusion, complex chemistry, and heterogeneous processes, in the interest of obtaining sensitivity-related information. The sensitivity equations were decoupled from those of the model, and then integrated one time-step behind the integration of the model equations, and analytical Jacobian matrices were applied to improve the accuracy of sensitivity coefficients that are calculated together with model solutions.

Poisson-Fermi modeling of ion activities in aqueous single and mixed electrolyte solutions at variable temperature

Science.gov (United States)

Liu, Jinn-Liang; Eisenberg, Bob

2018-02-01

The combinatorial explosion of empirical parameters in tens of thousands presents a tremendous challenge for extended Debye-Hückel models to calculate activity coefficients of aqueous mixtures of the most important salts in chemistry. The explosion of parameters originates from the phenomenological extension of the Debye-Hückel theory that does not take steric and correlation effects of ions and water into account. By contrast, the Poisson-Fermi theory developed in recent years treats ions and water molecules as nonuniform hard spheres of any size with interstitial voids and includes ion-water and ion-ion correlations. We present a Poisson-Fermi model and numerical methods for calculating the individual or mean activity coefficient of electrolyte solutions with any arbitrary number of ionic species in a large range of salt concentrations and temperatures. For each activity-concentration curve, we show that the Poisson-Fermi model requires only three unchanging parameters at most to well fit the corresponding experimental data. The three parameters are associated with the Born radius of the solvation energy of an ion in electrolyte solution that changes with salt concentrations in a highly nonlinear manner.

Solute-matrix and Solute-Solute Interactions during Supercritical Fluid Extraction of Sea Buckthorn Leaves

Czech Academy of Sciences Publication Activity Database

Sajfrtová, Marie; Sovová, Helena

2012-01-01

Roč. 42, SI (2012), s. 1682-1691 E-ISSN 1877-7058. [International Congress of Chemical and Process Engineering CHISA 2012 and 15th Conference PRES 2012 /20./. Prague, 25.08.2012-29.08.2012] R&D Projects: GA TA ČR TA01010578 Institutional support: RVO:67985858 Keywords : supercritical fluid extraction * sea buckthom leaves * solute-solute interaction Subject RIV: CI - Industrial Chemistry, Chemical Engineering

Modeling Human Serum Albumin Tertiary Structure to Teach Upper-Division Chemistry Students Bioinformatics and Homology Modeling Basics

Science.gov (United States)

Petrovic, Dus?an; Zlatovic´, Mario

2015-01-01

A homology modeling laboratory experiment has been developed for an introductory molecular modeling course for upper-division undergraduate chemistry students. With this experiment, students gain practical experience in homology model preparation and assessment as well as in protein visualization using the educational version of PyMOL…

Calibration of a Chemistry Test Using the Rasch Model

Directory of Open Access Journals (Sweden)

Nancy Coromoto Martín Guaregua

2011-11-01

Full Text Available The Rasch model was used to calibrate a general chemistry test for the purpose of analyzing the advantages and information the model provides. The sample was composed of 219 college freshmen. Of the 12 questions used, good fit was achieved in 10. The evaluation shows that although there are items of variable difficulty, there are gaps on the scale; in order to make the test complete, it will be necessary to design new items to fill in these gaps.

Radiation chemistry and its application

International Nuclear Information System (INIS)

Majima, Tetsuro

2013-01-01

Effects of radiation to human body have been seriously discussed nowadays. These are important issues for the realization of sustainable society. It should be emphasized that various reactive intermediates generated by radiation play important roles in each cases. Radiation chemical studies will provide various reaction-mechanistic aspects on these important issues. Our research group has continuously carried out reaction-mechanistic studies using radiation chemical methods. From these studies, we have obtained a variety of results on basic molecular systems, reactions, materials that are close to practical application, biological systems and so on. Reactive species are generated from the radiation reactions in solution, and can be used as one-electron oxidative and reductive reagent to give selectively radical cation and anion of solute molecules such as various organic and inorganic molecules. Therefore, the radiation chemistry has contributed significantly to chemistry in which one-electron oxidation and reduction play the important role. The kinetics of such redox processes and the following reduction play the important role. The kinetics of such redox processes and the following reactions can be studied in real time with the transition absorption measurement by the pulse radiolysis technique. Even though the target compounds cannot be oxidized and reduced in chemical or electrochemical oxidation and reduction, their one-electron redox can be performed by the electron beam radiation. Therefore, radiation chemistry is very useful technique for basic science. Moreover, application potentials of radiation chemistry are so high for various research subjects. Moreover, application potentials of radiation chemistry are so high for various research subjects

Tracking chemistry self-efficacy and achievement in a preparatory chemistry course

Science.gov (United States)

Garcia, Carmen Alicia

Self-efficacy is a person's own perception about performing a task with a certain level of proficiency (Bandura, 1986). An important affective aspect of learning chemistry is chemistry self-efficacy (CSE). Several researchers have found chemistry self-efficacy to be a fair predictor of achievement in chemistry. This study was done in a college preparatory chemistry class for science majors exploring chemistry self-efficacy and its change as it relates to achievement. A subscale of CAEQ, Chemistry Attitudes and Experiences Questionnaire (developed by Dalgety et al, 2003) as well as student interviews were used to determine student chemistry self-efficacy as it changed during the course. The questionnaire was given to the students five times during the semester: in the first class and the class before each the four tests taken through the semester. Twenty-six students, both men and women, of the four major races/ethnicities were interviewed three times during the semester and events that triggered changes in CSE were followed through the interviews. HLM (hierarchical linear modeling) was used to model the results of the CSE surveys. Among the findings, women who started at significantly lower CSE than men accomplished a significant gain by the end of the semester. Blacks' CSE trends through the semester were found to be significantly different from the rest of the ethnicities.

A new 2D climate model with chemistry and self consistent eddy-parameterization. The impact of airplane NO{sub x} on the chemistry of the atmosphere

Energy Technology Data Exchange (ETDEWEB)

Gepraegs, R.; Schmitz, G.; Peters, D. [Institut fuer Atmosphaerenphysik, Kuehlungsborn (Germany)

1997-12-31

A 2D version of the ECHAM T21 climate model has been developed. The new model includes an efficient spectral transport scheme with implicit diffusion. Furthermore, photodissociation and chemistry of the NCAR 2D model have been incorporated. A self consistent parametrization scheme is used for eddy heat- and momentum flux in the troposphere. It is based on the heat flux parametrization of Branscome and mixing-length formulation for quasi-geostrophic vorticity. Above 150 hPa the mixing-coefficient K{sub yy} is prescribed. Some of the model results are discussed, concerning especially the impact of aircraft NO{sub x} emission on the model chemistry. (author) 6 refs.

A new 2D climate model with chemistry and self consistent eddy-parameterization. The impact of airplane NO{sub x} on the chemistry of the atmosphere

Energy Technology Data Exchange (ETDEWEB)

Gepraegs, R; Schmitz, G; Peters, D [Institut fuer Atmosphaerenphysik, Kuehlungsborn (Germany)

1998-12-31

A 2D version of the ECHAM T21 climate model has been developed. The new model includes an efficient spectral transport scheme with implicit diffusion. Furthermore, photodissociation and chemistry of the NCAR 2D model have been incorporated. A self consistent parametrization scheme is used for eddy heat- and momentum flux in the troposphere. It is based on the heat flux parametrization of Branscome and mixing-length formulation for quasi-geostrophic vorticity. Above 150 hPa the mixing-coefficient K{sub yy} is prescribed. Some of the model results are discussed, concerning especially the impact of aircraft NO{sub x} emission on the model chemistry. (author) 6 refs.

Chemistry in CESM-SE: Evaluation, Performance and Optimization

Energy Technology Data Exchange (ETDEWEB)

Lamarque, Jean-Francois [National Center for Atmospheric Research, Boulder, CO (United States); Conley, Andrew [National Center for Atmospheric Research, Boulder, CO (United States); Vitt, Francis [National Center for Atmospheric Research, Boulder, CO (United States); Drake, John [Univ. of Tennessee, Knoxville, TN (United States); Sun, Jian [Univ. of Tennessee, Knoxville, TN (United States)

2016-01-06

The purpose of the proposed work focused on development of chemistry representation within the Spectral Element (SE) dynamical core as implemented in the Community Earth System Model (CESM). More specifically, a main focus was on the ability of SE to accurately represent tracer transport. The proposed approach was to incrementally increase the complexity of the problem, starting from specified two-dimensional flow and tracers to simulations using specified dynamics and full chemistry. As demonstrated below, we have successfully studied all aspects of the proposed work, although only part of the work has been published in the refereed literature so far. Furthermore, because the SE dynamical core has been found to have several deficiencies that are still being investigated for solution, not all proposed tasks were finalized. In addition to the tests for SE performance, in an effort to decrease the computational burden of interactive chemistry, especially in the case of a large number of chemical species and chemical reactions, development on a faster chemical solver and implementation on GPUs has been implemented in CESM under the leadership of John Drake (U. Tennessee).

Differences in soil solution chemistry between soils amended with nanosized CuO or Cu reference materials: implications for nanotoxicity tests.

Science.gov (United States)

McShane, Heather V A; Sunahara, Geoffrey I; Whalen, Joann K; Hendershot, William H

2014-07-15

Soil toxicity tests for metal oxide nanoparticles often include micrometer-sized oxide and metal salt treatments to distinguish between toxicity from nanometer-sized particles, non-nanometer-sized particles, and dissolved ions. Test result will be confounded if each chemical form has different effects on soil solution chemistry. We report on changes in soil solution chemistry over 56 days-the duration of some standard soil toxicity tests-in three soils amended with 500 mg/kg Cu as nanometer-sized CuO (nano), micrometer-sized CuO (micrometer), or Cu(NO3)2 (salt). In the CuO-amended soils, the log Cu2+ activity was initially low (minimum -9.48) and increased with time (maximum -5.20), whereas in the salt-amended soils it was initially high (maximum -4.80) and decreased with time (minimum -6.10). The Cu2+ activity in the nano-amended soils was higher than in the micrometer-amended soils for at least the first 11 days, and lower than in the salt-amended soils for at least 28 d. The pH, and dissolved Ca and Mg concentrations in the CuO-amended soils were similar, but the salt-amended soils had lower pH for at least 14 d, and higher Ca and Mg concentrations throughout the test. Soil pretreatments such as leaching and aging prior to toxicity tests are suggested.

Molybdenum (VI) binded to humic and nitrohumic acid models in aqueous solutions salicylic, 3-nitrosalicylic, 5-nitrosalicylic and 3,5 dinitrosalicylic acids, Part 2

International Nuclear Information System (INIS)

Merce, Ana Lucia R.; Lopes, Priscilla P.; Mangricha, Antonio S.

2006-01-01

In this work electrochemical and Ultraviolet-Visible studies were performed in solutions of salicylic acid models of humic and nitrohumic acids, a laboratory artifact, and molybdenum in order to determine the affinity of these models towards the metal ion. Molybdenum, which plays a very important role in the soil chemistry, and together with humic substances, impart fertility to soil and water and is a key element in the activity of nitrogenase. The obtained results showed that at least one complexed species is present at the pH range of 6.3 to 8.0, even for the less basic chosen models, the nitrosalicylic acids. Previous study showed that phthalic and nitrophthalic, also humic and nitrohumic acids model compounds, presented complexed species with molybdenum only till pH 6.5. The calculated formation constants showed that the substitution of the nitro group in the orto position was less favoured than in the para substitution, probably due to a steric hindrance in the former, which was clearly seen in the double substituted salicylic nitro derivative. The cyclic voltammetry as well as the Ultraviolet-Visible obtained spectra were able to show that the chemistry of molybdenum in aqueous solutions as the pH is increased is very complex, and the molybdate stops acting as an anion only after pH around 4, when it finally becomes a cation MoO 2 2+ (M). (author)

Some applications of radiation chemistry to biochemistry and radiobiology

International Nuclear Information System (INIS)

Wardman, P.

1987-01-01

In this chapter illustrate the use of radiation chemistry as a tool in investigating biologically important radical reactions, and also outline some studies of models for radiobiological damage. Because aqueous solutions usually offer the most important matrix, an appreciation of the main features of water radiolysis will be essential. Most of the illustrations involve pulse radiolysis, and some familiarity with chemical kinetics is assumed. In addition to these and other chapters in this book, readers find the proceedings of a recent NATO Advanced Study Institute most useful. The authors shall not try to review here all the applications of radiation chemistry to biochemistry and biology, but they will illustrate, using selected examples, the main principles and practical advantages and problems. Another recent volume covers the main contributions of flash photolysis and pulse radiolysis to the chemistry of biology and medicine, complementing earlier reviews. Papers from symposia on radical processes in radiobiology and carcinogenesis, and on super-oxide dismutases, and proceedings of recent international congresses of radiation research, together with the other publications referred to above will enable the reader to gain a comprehensive overview of the role of radicals in biological processes and the contributions of radiation chemistry

A comparison of amorphous calcium carbonate crystallization in aqueous solutions of MgCl2 and MgSO4: implications for paleo-ocean chemistry

Science.gov (United States)

Han, Mei; Zhao, Yanyang; Zhao, Hui; Han, Zuozhen; Yan, Huaxiao; Sun, Bin; Meng, Ruirui; Zhuang, Dingxiang; Li, Dan; Liu, Binwei

2018-04-01

Based on the terminology of "aragonite seas" and "calcite seas", whether different Mg sources could affect the mineralogy of carbonate sediments at the same Mg/Ca ratio was explored, which was expected to provide a qualitative assessment of the chemistry of the paleo-ocean. In this work, amorphous calcium carbonate (ACC) was prepared by direct precipitation in anhydrous ethanol and used as a precursor to study crystallization processes in MgSO4 and MgCl2 solutions having different concentrations at 60 °C (reaction times 240 and 2880 min). Based on the morphology of the aragonite crystals, as well as mineral saturation indices and kinetic analysis of geochemical processes, it was found that these crystals formed with a spherulitic texture in 4 steps. First, ACC crystallized into columnar Mg calcite by nearly oriented attachment. Second, the Mg calcite changed from columnar shapes into smooth dumbbell forms. Third, the Mg calcite transformed into rough dumbbell or cauliflower-shaped aragonite forms by local dissolution and precipitation. Finally, the aragonite transformed further into spherulitic radial and irregular aggregate forms. The increase in Ca2+ in the MgSO4 solutions compared with the MgCl2 solutions indicates the fast dissolution and slow precipitation of ACC in the former solutions. The phase transition was more complete in the 0.005 M MgCl2 solution, whereas Mg calcite crystallized from the 0.005 M MgSO4 solution, indicating that Mg calcite could be formed more easily in an MgSO4 solution. Based on these findings, aragonite and Mg calcite relative to ACC could be used to provide a qualitative assessment of the chemistry of the paleo-ocean. Therefore, calcite seas relative to high-Mg calcite could reflect a low concentration MgSO4 paleo-ocean, while aragonite seas could be related to an MgCl2 or high concentration of MgSO4 paleo-ocean.

Ground-water solute transport modeling using a three-dimensional scaled model

International Nuclear Information System (INIS)

Crider, S.S.

1987-01-01

Scaled models are used extensively in current hydraulic research on sediment transport and solute dispersion in free surface flows (rivers, estuaries), but are neglected in current ground-water model research. Thus, an investigation was conducted to test the efficacy of a three-dimensional scaled model of solute transport in ground water. No previous results from such a model have been reported. Experiments performed on uniform scaled models indicated that some historical problems (e.g., construction and scaling difficulties; disproportionate capillary rise in model) were partly overcome by using simple model materials (sand, cement and water), by restricting model application to selective classes of problems, and by physically controlling the effect of the model capillary zone. Results from these tests were compared with mathematical models. Model scaling laws were derived for ground-water solute transport and used to build a three-dimensional scaled model of a ground-water tritium plume in a prototype aquifer on the Savannah River Plant near Aiken, South Carolina. Model results compared favorably with field data and with a numerical model. Scaled models are recommended as a useful additional tool for prediction of ground-water solute transport

Connections between radiation and positronium chemistry

International Nuclear Information System (INIS)

Hirade, Tetsuya

2007-01-01

Some of the important connections between radiation chemistry and positronium chemistry started from the establishment of the spur reaction model proposed by Mogensen. Now, the modified model, the blob model proposed by Stepanov and Byakov, is making it possible to have the quantitative or semi-quantitative view of the positronium formation by using the distributions of positrons and excess electrons. Some of the interesting topics will be picked up here to understand the connections between radiation chemistry and positronium chemistry

Effects of Rhenium Addition on the Temporal Evolution of the Nanostructure and Chemistry of a Model Ni-Cr-Al Superalloy. 2; Analysis of the Coarsening Behavior

Science.gov (United States)

Yoon, Kevin E.; Noebe, Ronald D.; Seidman, David N.

2007-01-01

The temporal evolution of the nanostructure and chemistry of a model Ni-8.5 at.% Cr-10 at.% Al alloy with the addition of 2 at.% Re was studied using transmission electron microscopy and atom-probe tomography in order to measure the number density and mean radius of the y' (LIZ) precipitates and the chemistry of the y'-precipitates and the y (fcc)-matrix. In this article, the coarsening behavior of the y'-precipitates is discussed in detail and compared with the Umantsev-Olson model for multi-component alloys. In addition, the experimental results are evaluated with PrecipiCalc(TradeMark) simulations. The results show that the diffusivities of the solute elements play a major role in the coarsening behavior of the y'-precipitates and that the addition of Re retards the coarsening kinetics and stabilizes the spheroidal morphology of the precipitates by reducing the interfacial energy.

Non-uniform Solute Segregation at Semi-Coherent Metal/Oxide Interfaces

Science.gov (United States)

Choudhury, Samrat; Aguiar, Jeffery A.; Fluss, Michael J.; Hsiung, Luke L.; Misra, Amit; Uberuaga, Blas P.

2015-08-01

The properties and performance of metal/oxide nanocomposites are governed by the structure and chemistry of the metal/oxide interfaces. Here we report an integrated theoretical and experimental study examining the role of interfacial structure, particularly misfit dislocations, on solute segregation at a metal/oxide interface. We find that the local oxygen environment, which varies significantly between the misfit dislocations and the coherent terraces, dictates the segregation tendency of solutes to the interface. Depending on the nature of the solute and local oxygen content, segregation to misfit dislocations can change from attraction to repulsion, revealing the complex interplay between chemistry and structure at metal/oxide interfaces. These findings indicate that the solute chemistry at misfit dislocations is controlled by the dislocation density and oxygen content. Fundamental thermodynamic concepts - the Hume-Rothery rules and the Ellingham diagram - qualitatively predict the segregation behavior of solutes to such interfaces, providing design rules for novel interfacial chemistries.

An exploratory study of proficient undergraduate Chemistry II students' application of Lewis's model

Science.gov (United States)

Lewis, Sumudu R.

This exploratory study was based on the assumption that proficiency in chemistry must not be determined exclusively on students' declarative and procedural knowledge, but it should be also described as the ability to use variety of reasoning strategies that enrich and diversify procedural methods. The study furthermore assumed that the ability to describe the structure of a molecule using Lewis's model and use it to predict its geometry as well as some of its properties is indicative of proficiency in the essential concepts of covalent bonding and molecule structure. The study therefore inquired into the reasoning methods and procedural techniques of proficient undergraduate Chemistry II students when solving problems, which require them to use Lewis's model. The research design included an original survey, designed by the researcher for this study, and two types of interviews, with students and course instructors. The purpose of the survey was two-fold. First and foremost, the survey provided a base for the student interview selection, and second it served as the foundation for the inquiry into the strategies the student use when solving survey problems. Twenty two students were interviewed over the course of the study. The interview with six instructors allowed to identify expected prior knowledge and skills, which the students should have acquired upon completion of the Chemistry I course. The data, including videos, audios, and photographs of the artifacts produced by students during the interviews, were organized and analyzed manually and using QSR NVivo 10. The research found and described the differences between proficient and non-proficient students' reasoning and procedural strategies when using Lewis's model to describe the structure of a molecule. One of the findings clearly showed that the proficient students used a variety of cues to reason, whereas other students used one memorized cue, or an algorithm, which often led to incorrect representations in

Numerical Modeling of Climate-Chemistry Connections: Recent Developments and Future Challenges

Directory of Open Access Journals (Sweden)

Patrick Jöckel

2013-05-01

Full Text Available This paper reviews the current state and development of different numerical model classes that are used to simulate the global atmospheric system, particularly Earth’s climate and climate-chemistry connections. The focus is on Chemistry-Climate Models. In general, these serve to examine dynamical and chemical processes in the Earth atmosphere, their feedback, and interaction with climate. Such models have been established as helpful tools in addition to analyses of observational data. Definitions of the global model classes are given and their capabilities as well as weaknesses are discussed. Examples of scientific studies indicate how numerical exercises contribute to an improved understanding of atmospheric behavior. There, the focus is on synergistic investigations combining observations and model results. The possible future developments and challenges are presented, not only from the scientific point of view but also regarding the computer technology and respective consequences for numerical modeling of atmospheric processes. In the future, a stronger cross-linkage of subject-specific scientists is necessary, to tackle the looming challenges. It should link the specialist discipline and applied computer science.

A review of the radiation chemistry of iodine compounds in aqueous solution

International Nuclear Information System (INIS)

Sellers, R.M.

1977-06-01

Large amounts of radioactive iodine are formed in the fission of uranium in nuclear reactors. Some of this may be released to the coolant from the fuel either by diffusion through the canning material, or following the failure of a fuel pin. The iodine, which is released mainly as I 2 and methyl iodide, is transported with the coolant and, in direct cycle water cooled reactors, some is carried over with the steam to the turbines, where contamination may build up in the vicinity of steam leaks. Any assessment of the mechanism of the transport of iodine requires a knowledge of the relative amounts of the various oxidation states present, and must consider not only the thermal behaviour of iodine in water, but also the radiation chemical effects. A review is presented of the radiation chemistry of inorganic iodine compounds and methyl iodide in aqueous solutions. A number of unstable intermediates have been identified including species with iodide in valency states II, IV, VI and VIII. A considerable number of discrepancies exist in the literature data, and requirements for further work are identified. (author)

Metadynamics for training neural network model chemistries: A competitive assessment

Science.gov (United States)

Herr, John E.; Yao, Kun; McIntyre, Ryker; Toth, David W.; Parkhill, John

2018-06-01

Neural network model chemistries (NNMCs) promise to facilitate the accurate exploration of chemical space and simulation of large reactive systems. One important path to improving these models is to add layers of physical detail, especially long-range forces. At short range, however, these models are data driven and data limited. Little is systematically known about how data should be sampled, and "test data" chosen randomly from some sampling techniques can provide poor information about generality. If the sampling method is narrow, "test error" can appear encouragingly tiny while the model fails catastrophically elsewhere. In this manuscript, we competitively evaluate two common sampling methods: molecular dynamics (MD), normal-mode sampling, and one uncommon alternative, Metadynamics (MetaMD), for preparing training geometries. We show that MD is an inefficient sampling method in the sense that additional samples do not improve generality. We also show that MetaMD is easily implemented in any NNMC software package with cost that scales linearly with the number of atoms in a sample molecule. MetaMD is a black-box way to ensure samples always reach out to new regions of chemical space, while remaining relevant to chemistry near kbT. It is a cheap tool to address the issue of generalization.

Computational Modeling of the Optical Rotation of Amino Acids: An "in Silico" Experiment for Physical Chemistry

Science.gov (United States)

Simpson, Scott; Autschbach, Jochen; Zurek, Eva

2013-01-01

A computational experiment that investigates the optical activity of the amino acid valine has been developed for an upper-level undergraduate physical chemistry laboratory course. Hybrid density functional theory calculations were carried out for valine to confirm the rule that adding a strong acid to a solution of an amino acid in the l…

Variational data assimilation schemes for transport and transformation models of atmospheric chemistry

Science.gov (United States)

Penenko, Alexey; Penenko, Vladimir; Tsvetova, Elena; Antokhin, Pavel

2016-04-01

The work is devoted to data assimilation algorithm for atmospheric chemistry transport and transformation models. In the work a control function is introduced into the model source term (emission rate) to provide flexibility to adjust to data. This function is evaluated as the constrained minimum of the target functional combining a control function norm with a norm of the misfit between measured data and its model-simulated analog. Transport and transformation processes model is acting as a constraint. The constrained minimization problem is solved with Euler-Lagrange variational principle [1] which allows reducing it to a system of direct, adjoint and control function estimate relations. This provides a physically-plausible structure of the resulting analysis without model error covariance matrices that are sought within conventional approaches to data assimilation. High dimensionality of the atmospheric chemistry models and a real-time mode of operation demand for computational efficiency of the data assimilation algorithms. Computational issues with complicated models can be solved by using a splitting technique. Within this approach a complex model is split to a set of relatively independent simpler models equipped with a coupling procedure. In a fine-grained approach data assimilation is carried out quasi-independently on the separate splitting stages with shared measurement data [2]. In integrated schemes data assimilation is carried out with respect to the split model as a whole. We compare the two approaches both theoretically and numerically. Data assimilation on the transport stage is carried out with a direct algorithm without iterations. Different algorithms to assimilate data on nonlinear transformation stage are compared. In the work we compare data assimilation results for both artificial and real measurement data. With these data we study the impact of transformation processes and data assimilation to the performance of the modeling system [3]. The

Existence of Periodic Solutions and Stability of Zero Solution of a Mathematical Model of Schistosomiasis

Directory of Open Access Journals (Sweden)

Lin Li

2014-01-01

Full Text Available A mathematical model on schistosomiasis governed by periodic differential equations with a time delay was studied. By discussing boundedness of the solutions of this model and construction of a monotonic sequence, the existence of positive periodic solution was shown. The conditions under which the model admits a periodic solution and the conditions under which the zero solution is globally stable are given, respectively. Some numerical analyses show the conditional coexistence of locally stable zero solution and periodic solutions and that it is an effective treatment by simply reducing the population of snails and enlarging the death ratio of snails for the control of schistosomiasis.

Potential alteration of precipitation chemistry by epiphytic lichens

Energy Technology Data Exchange (ETDEWEB)

Lang, G E; Reiners, W A; Heier, R K

1976-01-01

Epiphytic lichen growth is abundant on the boles and branches of balsam fir trees at high elevations in New Hampshire. These lichens absorb elements needed for growth from solutions flowing over their surfaces and from direct impaction of water droplets. This study describes how epiphytic lichens and fir needles altered the chemistry of simulated rain water solutions under laboratory conditions. Experiments showed: 1) lichens absorbed ammonium and nitrate from solution; the rate of uptake increased with increasing temperature of the solution, 2) lichens lost calcium, magnesium, and hydrogen to the solution, 3) lichen thalli also initially lost potassium, but in time, net movement was reversed back into the thallus, 4) cation movement increased with increasing temperature, and 5) fir needles responded in a manner similar to that of the lichens, but the amount of change was much less. From these results it seems that epiphytic lichens have potential ecological importance in altering the chemistry of throughfall and stemflow.

Integration of Information Literacy Components into a Large First-Year Lecture-Based Chemistry Course

Science.gov (United States)

Locknar, Angela; Mitchell, Rudolph; Rankin, Janet; Sadoway, Donald R.

2012-01-01

A first-year chemistry course is ideal for introducing students to finding and using scholarly information early in their academic careers. A four-pronged approach (lectures, homework problems, videos, and model solutions) was used to incorporate library research skills into a large lecture-based course. Pre- and post-course surveying demonstrated…

High-Latitude Stratospheric Sensitivity to QBO Width in a Chemistry-Climate Model with Parameterized Ozone Chemistry

Science.gov (United States)

Hurwitz, M. M.; Braesicke, P.; Pyle, J. A.

2010-01-01

In a pair of idealized simulations with a simplified chemistry-climate model, the sensitivity of the wintertime Arctic stratosphere to variability in the width of the quasi-biennial oscillation (QBO) is assessed. The width of the QBO appears to have equal influence on the Arctic stratosphere as does the phase (i.e. the Holton-Tan mechanism). In the model, a wider QBO acts like a preferential shift toward the easterly phase of the QBO, where zonal winds at 60 N tend to be relatively weaker, while 50 hPa geopotential heights and polar ozone values tend to be higher.

The response of soil solution chemistry in European forests to decreasing acid deposition.

Science.gov (United States)

Johnson, James; Graf Pannatier, Elisabeth; Carnicelli, Stefano; Cecchini, Guia; Clarke, Nicholas; Cools, Nathalie; Hansen, Karin; Meesenburg, Henning; Nieminen, Tiina M; Pihl-Karlsson, Gunilla; Titeux, Hugues; Vanguelova, Elena; Verstraeten, Arne; Vesterdal, Lars; Waldner, Peter; Jonard, Mathieu

2018-03-31

Acid deposition arising from sulphur (S) and nitrogen (N) emissions from fossil fuel combustion and agriculture has contributed to the acidification of terrestrial ecosystems in many regions globally. However, in Europe and North America, S deposition has greatly decreased in recent decades due to emissions controls. In this study, we assessed the response of soil solution chemistry in mineral horizons of European forests to these changes. Trends in pH, acid neutralizing capacity (ANC), major ions, total aluminium (Al tot ) and dissolved organic carbon were determined for the period 1995-2012. Plots with at least 10 years of observations from the ICP Forests monitoring network were used. Trends were assessed for the upper mineral soil (10-20 cm, 104 plots) and subsoil (40-80 cm, 162 plots). There was a large decrease in the concentration of sulphate (SO42-) in soil solution; over a 10-year period (2000-2010), SO42- decreased by 52% at 10-20 cm and 40% at 40-80 cm. Nitrate was unchanged at 10-20 cm but decreased at 40-80 cm. The decrease in acid anions was accompanied by a large and significant decrease in the concentration of the nutrient base cations: calcium, magnesium and potassium (Bc = Ca 2+  + Mg 2+  + K + ) and Al tot over the entire dataset. The response of soil solution acidity was nonuniform. At 10-20 cm, ANC increased in acid-sensitive soils (base saturation ≤10%) indicating a recovery, but ANC decreased in soils with base saturation >10%. At 40-80 cm, ANC remained unchanged in acid-sensitive soils (base saturation ≤20%, pHCaCl2 ≤ 4.5) and decreased in better-buffered soils (base saturation >20%, pHCaCl2 > 4.5). In addition, the molar ratio of Bc to Al tot either did not change or decreased. The results suggest a long-time lag between emission abatement and changes in soil solution acidity and underline the importance of long-term monitoring in evaluating ecosystem response to decreases in deposition. © 2018 John Wiley & Sons

A Wet Chemistry Laboratory Cell

Science.gov (United States)

2008-01-01

This picture of NASA's Phoenix Mars Lander's Wet Chemistry Laboratory (WCL) cell is labeled with components responsible for mixing Martian soil with water from Earth, adding chemicals and measuring the solution chemistry. WCL is part of the Microscopy, Electrochemistry, and Conductivity Analyzer (MECA) instrument suite on board the Phoenix lander. The Phoenix Mission is led by the University of Arizona, Tucson, on behalf of NASA. Project management of the mission is by NASA's Jet Propulsion Laboratory, Pasadena, Calif. Spacecraft development is by Lockheed Martin Space Systems, Denver.

Multi-cut solutions in Chern-Simons matrix models

Science.gov (United States)

Morita, Takeshi; Sugiyama, Kento

2018-04-01

We elaborate the Chern-Simons (CS) matrix models at large N. The saddle point equations of these matrix models have a curious structure which cannot be seen in the ordinary one matrix models. Thanks to this structure, an infinite number of multi-cut solutions exist in the CS matrix models. Particularly we exactly derive the two-cut solutions at finite 't Hooft coupling in the pure CS matrix model. In the ABJM matrix model, we argue that some of multi-cut solutions might be interpreted as a condensation of the D2-brane instantons.

Integrating chemistry into 3D climate models: Detailed kinetics in the troposphere and stratosphere of a global climate model

Energy Technology Data Exchange (ETDEWEB)

Kao, C.Y.J.; Elliott, S. [Los Alamos National Lab., NM (United States). Earth and Environmental Sciences Div.; Turco, R.P.; Zhao, X. [Univ. of California, Los Angeles, CA (United States)

1997-11-01

This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The motivation for the project is to create the first complete, three-dimensional climate model that enfolds atmospheric photochemistry. The LANL chemical global climate model (GCM) not only distributes the trace greenhouse gases and modifies their concentrations within the detailed photochemical web, but also permits them to influence the radiation field and so force their own transport. Both atmospheric chemistry and fluid dynamics are nonlinear and zonally asymmetric phenomena. They can only be adequately modeled in three dimensions on the global grid. The kinetics-augmented GCM is the only program within the atmospheric community capable of investigating interaction involving chemistry and transport. The authors have conducted case studies of timely three-dimensional chemistry issues. Examples include ozone production from biomass burning plumes, kinetic feedbacks in zonally asymmetric transport phenomena with month- to year-long time scales, and volcano sulfate aerosols with respect to their potential effects on tropospheric ozone depletion.

College Chemistry Students' Mental Models of Acids and Acid Strength

Science.gov (United States)

McClary, LaKeisha; Talanquer, Vicente

2011-01-01

The central goal of this study was to characterize the mental models of acids and acid strength expressed by advanced college chemistry students when engaged in prediction, explanation, and justification tasks that asked them to rank chemical compounds based on their relative acid strength. For that purpose we completed a qualitative research…

Fuel Chemistry Division: progress report for 1985

International Nuclear Information System (INIS)

1988-01-01

Fuel Chemistry Division was formed in May 1985 to give a larger emphasis on the research and development in chemistry of the nuclear fuel cycle. The areas of research in Fuel Chemistry Division are fuel development and its chemical quality control, understanding of the fuel behaviour and post irradiation examinations, chemistry of reprocessing and waste management processes as also the basic aspects of actinide and relevant fission product elements. This report summarises the work by the staff of the Division during 1985 and also some work from the previous periods which was not reported in the progress reports of the Radiochemistry Division. The work related to the FBTR fuel was one of the highlights during this period. In the area of process chemistry useful work has been carried out for processing of plutonium bearing solutions. In the area of mass spectrometry, the determination of trace constituents by spark source mass spectrometry has been a major area of research. Significant progress has also been made in the use of alpha spectromet ry techniques for the determination of plutonium in dissolver solution and other samples. The technology of plutonium utilisation is quite complex and the Division would continue to look into the chemical aspects of this technology and provide the necessary base for future developments in this area. (author)

Applied Integer Programming Modeling and Solution

CERN Document Server

Chen, Der-San; Dang, Yu

2011-01-01

An accessible treatment of the modeling and solution of integer programming problems, featuring modern applications and software In order to fully comprehend the algorithms associated with integer programming, it is important to understand not only how algorithms work, but also why they work. Applied Integer Programming features a unique emphasis on this point, focusing on problem modeling and solution using commercial software. Taking an application-oriented approach, this book addresses the art and science of mathematical modeling related to the mixed integer programming (MIP) framework and

Skyrmion solutions to the Weinberg-Salam model

International Nuclear Information System (INIS)

Eilam, G.; Klabucar, D.; Stern, A.

1986-01-01

We find a spherically symmetric solution to the gauged SU(2)/sub L/ x SU(2)/sub R/ chiral model. It corresponds to a new classical solution to the Weinberg-Salam model in the limit of infinite self-coupling and sin 2 theta/sub W/ = 0. It has an energy of 11.6 TeV and is classically unstable under small perturbations of the fields. Quantum corrections may stabilize the solution via the introduction of higher-order terms in the effective action. We then investigate the solutions when a particular choice of a correction, the Skyrme term, is added to the Lagrangian. The energies of the (presumably) classically stable solutions are in the terraelectrovolt region

Why has the bohr-sommerfeld model of the atom been ignoredby general chemistry textbooks?

Science.gov (United States)

Niaz, Mansoor; Cardellini, Liberato

2011-12-01

Bohr's model of the atom is considered to be important by general chemistry textbooks. A major shortcoming of this model was that it could not explain the spectra of atoms containing more than one electron. In order to increase the explanatory power of the model, Sommerfeld hypothesized the existence of elliptical orbits. This study has the following objectives: 1) Formulation of criteria based on a history and philosophy of science framework; and 2) Evaluation of university-level general chemistry textbooks based on the criteria, published in Italy and U.S.A. Presentation of a textbook was considered to be "satisfactory" if it included a description of the Bohr-Sommerfeld model along with diagrams of the elliptical orbits. Of the 28 textbooks published in Italy that were analyzed, only five were classified as "satisfactory". Of the 46 textbooks published in U.S.A., only three were classified as "satisfactory". This study has the following educational implications: a) Sommerfeld's innovation (auxiliary hypothesis) by introducing elliptical orbits, helped to restore the viability of Bohr's model; b) Bohr-Sommerfeld's model went no further than the alkali metals, which led scientists to look for other models; c) This clearly shows that scientific models are tentative in nature; d) Textbook authors and chemistry teachers do not consider the tentative nature of scientific knowledge to be important; e) Inclusion of the Bohr-Sommerfeld model in textbooks can help our students to understand how science progresses.

Modelling iodide – iodate speciation in atmospheric aerosol: Contributions of inorganic and organic iodine chemistry

Directory of Open Access Journals (Sweden)

S. Pechtl

2007-01-01

Full Text Available The speciation of iodine in atmospheric aerosol is currently poorly understood. Models predict negligible iodide concentrations but accumulation of iodate in aerosol, both of which is not confirmed by recent measurements. We present an updated aqueous phase iodine chemistry scheme for use in atmospheric chemistry models and discuss sensitivity studies with the marine boundary layer model MISTRA. These studies show that iodate can be reduced in acidic aerosol by inorganic reactions, i.e., iodate does not necessarily accumulate in particles. Furthermore, the transformation of particulate iodide to volatile iodine species likely has been overestimated in previous model studies due to negligence of collision-induced upper limits for the reaction rates. However, inorganic reaction cycles still do not seem to be sufficient to reproduce the observed range of iodide – iodate speciation in atmospheric aerosol. Therefore, we also investigate the effects of the recently suggested reaction of HOI with dissolved organic matter to produce iodide. If this reaction is fast enough to compete with the inorganic mechanism, it would not only directly lead to enhanced iodide concentrations but, indirectly via speed-up of the inorganic iodate reduction cycles, also to a decrease in iodate concentrations. Hence, according to our model studies, organic iodine chemistry, combined with inorganic reaction cycles, is able to reproduce observations. The presented chemistry cycles are highly dependent on pH and thus offer an explanation for the large observed variability of the iodide – iodate speciation in atmospheric aerosol.

Spatially Resolved Artificial Chemistry

DEFF Research Database (Denmark)

Fellermann, Harold

2009-01-01

Although spatial structures can play a crucial role in chemical systems and can drastically alter the outcome of reactions, the traditional framework of artificial chemistry is a well-stirred tank reactor with no spatial representation in mind. Advanced method development in physical chemistry has...... made a class of models accessible to the realms of artificial chemistry that represent reacting molecules in a coarse-grained fashion in continuous space. This chapter introduces the mathematical models of Brownian dynamics (BD) and dissipative particle dynamics (DPD) for molecular motion and reaction...

Spatially Resolved Artificial Chemistry

DEFF Research Database (Denmark)

Fellermann, Harold

2009-01-01

made a class of models accessible to the realms of artificial chemistry that represent reacting molecules in a coarse-grained fashion in continuous space. This chapter introduces the mathematical models of Brownian dynamics (BD) and dissipative particle dynamics (DPD) for molecular motion and reaction......Although spatial structures can play a crucial role in chemical systems and can drastically alter the outcome of reactions, the traditional framework of artificial chemistry is a well-stirred tank reactor with no spatial representation in mind. Advanced method development in physical chemistry has...

Implementation and evaluation of pH-dependent cloud chemistry and wetdeposition in the chemical transport model REM-Calgrid

NARCIS (Netherlands)

Banzhaf, S.; Schaap, M.; Kerschbaumer, A.; Reimer, E.; Stern, R.; Swaluw, E. van der; Builtjes, P.

2012-01-01

The Chemistry Transport Model REM-Calgrid (RCG) has been improved by implementing an enhanced description of aqueous-phase chemistry and wet deposition processes including droplet pH. A sensitivity study on cloud and rain droplet pH has been performed to investigate its impact on model sulphate

porewater chemistry experiment at Mont Terri rock laboratory. Reactive transport modelling including bacterial activity

International Nuclear Information System (INIS)

Tournassat, Christophe; Gaucher, Eric C.; Leupin, Olivier X.; Wersin, Paul

2010-01-01

Document available in extended abstract form only. An in-situ test in the Opalinus Clay formation, termed pore water Chemistry (PC) experiment, was run for a period of five years. It was based on the concept of diffusive equilibration whereby traced water with a composition close to that expected in the formation was continuously circulated and monitored in a packed off borehole. The main original focus was to obtain reliable data on the pH/pCO 2 of the pore water, but because of unexpected microbially- induced redox reactions, the objective was then changed to elucidate the biogeochemical processes happening in the borehole and to understand their impact on pH/pCO 2 and pH in the low permeability clay formation. The biologically perturbed chemical evolution of the PC experiment was simulated with reactive transport models. The aim of this modelling exercise was to develop a 'minimal-' model able to reproduce the chemical evolution of the PC experiment, i.e. the chemical evolution of solute inorganic and organic compounds (organic carbon, dissolved inorganic carbon etc...) that are coupled with each other through the simultaneous occurrence of biological transformation of solute or solid compounds, in-diffusion and out-diffusion of solute species and precipitation/dissolution of minerals (in the borehole and in the formation). An accurate description of the initial chemical conditions in the surrounding formation together with simplified kinetics rule mimicking the different phases of bacterial activities allowed reproducing the evolution of all main measured parameters (e.g. pH, TOC). Analyses from the overcoring and these simulations evidence the high buffer capacity of Opalinus clay regarding chemical perturbations due to bacterial activity. This pH buffering capacity is mainly attributed to the carbonate system as well as to the clay surfaces reactivity. Glycerol leaching from the pH-electrode might be the primary organic source responsible for

Designing a Scalable Fault Tolerance Model for High Performance Computational Chemistry: A Case Study with Coupled Cluster Perturbative Triples.

Science.gov (United States)

van Dam, Hubertus J J; Vishnu, Abhinav; de Jong, Wibe A

2011-01-11

In the past couple of decades, the massive computational power provided by the most modern supercomputers has resulted in simulation of higher-order computational chemistry methods, previously considered intractable. As the system sizes continue to increase, the computational chemistry domain continues to escalate this trend using parallel computing with programming models such as Message Passing Interface (MPI) and Partitioned Global Address Space (PGAS) programming models such as Global Arrays. The ever increasing scale of these supercomputers comes at a cost of reduced Mean Time Between Failures (MTBF), currently on the order of days and projected to be on the order of hours for upcoming extreme scale systems. While traditional disk-based check pointing methods are ubiquitous for storing intermediate solutions, they suffer from high overhead of writing and recovering from checkpoints. In practice, checkpointing itself often brings the system down. Clearly, methods beyond checkpointing are imperative to handling the aggravating issue of reducing MTBF. In this paper, we address this challenge by designing and implementing an efficient fault tolerant version of the Coupled Cluster (CC) method with NWChem, using in-memory data redundancy. We present the challenges associated with our design, including an efficient data storage model, maintenance of at least one consistent data copy, and the recovery process. Our performance evaluation without faults shows that the current design exhibits a small overhead. In the presence of a simulated fault, the proposed design incurs negligible overhead in comparison to the state of the art implementation without faults.

Predictive geochemical modeling of uranium and other contaminants in laboratory columns in relatively oxidizing, carbonate-rich solutions

International Nuclear Information System (INIS)

Longmire, P.; Turney, W.R.; Mason, C.F.V.

1994-01-01

Carbonate heap leaching of uranium-contaminated soils and sediments represents a viable, cost-effective remediation technology. Column experiments have been conducted using 0.1, 0.25, and 0.5 M Na 2 CO 3 /NaHCO 3 solutions for leaching uranium from soils located adjacent to an incinerator at the Fernald Environmental Management Project (FEMP) site. Results from column experiments and geochemical modeling are used to quantitatively evaluate the effectiveness of heap leaching. Leach efficiencies of up to 72 wt.% of total uranium in CaO-agglomerated soil result from dissolution of uranium (U(VI)-dominated) minerals, formation of the soluble complex UO 2 (CO 3 ) 3 4- , and uranium desorption from clay minerals, ferric hydroxides, and humic acids. Parameters that control the extent of uranium extraction include pH, Eh, temperature, carbonate concentration, lixiviant-flow rate, pore-solution chemistry, solid phases, and soil texture

Molybdenum (VI binded to humic and nitrohumic acid models in aqueous solutions. Salicylic, 3-nitrosalicylic, 5-nitrosalicylic and 3,5 dinitrosalicylic acids: part 2

Directory of Open Access Journals (Sweden)

Mercê Ana Lucia R.

2006-01-01

Full Text Available In this work electrochemical and Ultraviolet-Visible studies were performed in solutions of salicylic acid models of humic and nitrohumic acids, a laboratory artifact, and molybdenum in order to determine the affinity of these models towards the metal ion. Molybdenum, which plays a very important role in the soil chemistry, and together with humic substances, impart fertility to soil and water and is a key element in the activity of nitrogenase. The obtained results showed that at least one complexed species is present at the pH range of 6.3 to 8.0, even for the less basic chosen models, the nitrosalicylic acids. Previous study showed that phthalic and nitrophthalic, also humic and nitrohumic acids model compounds, presented complexed species with molybdenum only till pH 6.5. The calculated formation constants showed that the substitution of the nitro group in the orto position was less favoured than in the para substitution, probably due to a steric hindrance in the former, which was clearly seen in the double substituted salicylic nitro derivative. The cyclic voltammetry as well as the Ultraviolet-Visible obtained spectra were able to show that the chemistry of molybdenum in aqueous solutions as the pH is increased is very complex, and the molybdate stops acting as an anion only after pH around 4, when it finally becomes a cation MoO2(2+ (M.

Nitrogen Compounds in Radiation Chemistry

International Nuclear Information System (INIS)

Sims, H.E.; Dey, G.R.; Vaudey, C.E.; Peaucelle, C.; Boucher, J.L.; Toulhoat, N.; Bererd, N.; Koppenol, W.H.; Janata, E.; Dauvois, V.; Durand, D.; Legand, S.; Roujou, J.L.; Doizi, D.; Dannoux, A.; Lamouroux, C.

2009-01-01

Water radiolysis in presence of N 2 is probably the topic the most controversy in the field of water radiolysis. It still exists a strong discrepancy between the different reports of ammonia formation by water radiolysis in presence of N 2 and moreover in absence of oxygen there is no agreement on the formation or not of nitrogen oxide like NO 2 - and NO 3 -. These discrepancies come from multiple sources: - the complexity of the reaction mechanisms where nitrogen is involved - the experimental difficulties - and, the irradiation conditions. The aim of the workshop is to capitalize the knowledge needed to go further in simulations and understanding the problems caused (or not) by the presence of nitrogen / water in the environment of radioactive materials. Implications are evident in terms of corrosion, understanding of biological systems and atmospheric chemistry under radiation. Topics covered include experimental and theoretical approaches, application and fundamental researches: - Nitrate and Ammonia in radiation chemistry in nuclear cycle; - NOx in biological systems and atmospheric chemistry; - Formation of Nitrogen compounds in Nuclear installations; - Nitrogen in future power plant projects (Gen4, ITER...) and large particle accelerators. This document gathers the transparencies available for 7 of the presentations given at this workshop. These are: - H.E SIMS: 'Radiation Chemistry of Nitrogen Compounds in Nuclear Power Plant'; - G.R. DEY: 'Nitrogen Compounds Formation in the Radiolysis of Aqueous Solutions'; - C.E. VAUDEY et al.: 'Radiolytic corrosion of nuclear graphite studied with the dedicated gas irradiation cell of IPNL'; - J.L. BOUCHER: 'Roles and biosynthesis of NO in eukaryotes and prokaryotes'; - W.H. KOPPENOL: 'Chemistry of NOx'; - E. JANATA: 'Yield of OH in N 2 O saturated aqueous solution'; - V. DAUVOIS: 'Analytical strategy for the study of radiolysis gases'

Computational Tools To Model Halogen Bonds in Medicinal Chemistry.

Science.gov (United States)

Ford, Melissa Coates; Ho, P Shing

2016-03-10

The use of halogens in therapeutics dates back to the earliest days of medicine when seaweed was used as a source of iodine to treat goiters. The incorporation of halogens to improve the potency of drugs is now fairly standard in medicinal chemistry. In the past decade, halogens have been recognized as direct participants in defining the affinity of inhibitors through a noncovalent interaction called the halogen bond or X-bond. Incorporating X-bonding into structure-based drug design requires computational models for the anisotropic distribution of charge and the nonspherical shape of halogens, which lead to their highly directional geometries and stabilizing energies. We review here current successes and challenges in developing computational methods to introduce X-bonding into lead compound discovery and optimization during drug development. This fast-growing field will push further development of more accurate and efficient computational tools to accelerate the exploitation of halogens in medicinal chemistry.

Application of fundamental aquatic chemistry to the safety case and the role of thermodynamic reference data bases

International Nuclear Information System (INIS)

Altmaier, Marcus; Gaona, Xavier; Fellhauer, David; Geckeis, Horst

2015-01-01

All national and international programs developing a Nuclear Waste Disposal Safety Case have recognized the essential requirement of assessing aqueous (radionuclide) chemistry and establishing reliable thermodynamic databases. Long-term disposal of nuclear waste in deep underground repositories is the safest option to separate highly hazardous radionuclides from the environment. In order to predict the long-term performance of a repository for different evolution scenarios, the potentially relevant specific (geo)chemical systems are analyzed. This requires a detailed understanding of solubility, speciation and thermodynamics for all relevant components including radionuclides, and the availability of reliable thermodynamic data and databases as fundamental input for integral geochemical model calculations and hence PA. Radionuclide solubility and speciation strongly depend on chemical conditions (pH, E h , matrix electrolyte system and ionic strength) with additional factors like the presence of complexing ligands or temperature further impacting solution chemistry. As the fundamental chemical key processes are known and convincingly described by general laws of nature (→ solution thermodynamics), the long-term behavior of a repository system can be analyzed over geological timescales using geochemical tools. A key application of fundamental aquatic chemistry in the Safety Case is the determination of solubility limits (radionuclide source terms). Based upon fundamental chemical information (on solid phases, complexation reactions, activity coefficients, etc.), the maximum amount of radionuclides potentially dissolved in a given volume of solution and transported away from the repository, are quantified. A detailed understanding of radionuclide chemistry is also crucial for neighboring fields. For example, advanced mechanistic understanding and modeling of sorption processes at the solid liquid interphase, waste dissolution processes, secondary phase and solid

Application of fundamental aquatic chemistry to the safety case and the role of thermodynamic reference data bases

Energy Technology Data Exchange (ETDEWEB)

Altmaier, Marcus; Gaona, Xavier; Fellhauer, David; Geckeis, Horst [Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen (Germany). Inst. for Nuclear Waste Disposal

2015-07-01

All national and international programs developing a Nuclear Waste Disposal Safety Case have recognized the essential requirement of assessing aqueous (radionuclide) chemistry and establishing reliable thermodynamic databases. Long-term disposal of nuclear waste in deep underground repositories is the safest option to separate highly hazardous radionuclides from the environment. In order to predict the long-term performance of a repository for different evolution scenarios, the potentially relevant specific (geo)chemical systems are analyzed. This requires a detailed understanding of solubility, speciation and thermodynamics for all relevant components including radionuclides, and the availability of reliable thermodynamic data and databases as fundamental input for integral geochemical model calculations and hence PA. Radionuclide solubility and speciation strongly depend on chemical conditions (pH, E{sub h}, matrix electrolyte system and ionic strength) with additional factors like the presence of complexing ligands or temperature further impacting solution chemistry. As the fundamental chemical key processes are known and convincingly described by general laws of nature (→ solution thermodynamics), the long-term behavior of a repository system can be analyzed over geological timescales using geochemical tools. A key application of fundamental aquatic chemistry in the Safety Case is the determination of solubility limits (radionuclide source terms). Based upon fundamental chemical information (on solid phases, complexation reactions, activity coefficients, etc.), the maximum amount of radionuclides potentially dissolved in a given volume of solution and transported away from the repository, are quantified. A detailed understanding of radionuclide chemistry is also crucial for neighboring fields. For example, advanced mechanistic understanding and modeling of sorption processes at the solid liquid interphase, waste dissolution processes, secondary phase and

Unconventional Constraints on Nitrogen Chemistry using DC3 Observations and Trajectory-based Chemical Modeling

Science.gov (United States)

Shu, Q.; Henderson, B. H.

2017-12-01

Chemical transport models underestimate nitrogen dioxide observations in the upper troposphere (UT). Previous research in the UT succeeded in combining model predictions with field campaign measurements to demonstrate that the nitric acid formation rate (HO + NO2 → HNO3 (R1)) is overestimated by 22% (Henderson et al., 2012). A subsequent publication (Seltzer et al., 2015) demonstrated that single chemical constraint alters ozone and aerosol formation/composition. This work attempts to replicate previous chemical constraints with newer observations and a different modeling framework. We apply the previously successful constraint framework to Deep Convection Clouds and Chemistry (DC3). DC3 is a more recent field campaign where simulated nitrogen imbalances still exist. Freshly convected air parcels, identified in the DC3 dataset, as initial coordinates to initiate Lagrangian trajectories. Along each trajectory, we simulate the air parcel chemical state. Samples along the trajectories will form ensembles that represent possible realizations of UT air parcels. We then apply Bayesian inference to constrain nitrogen chemistry and compare results to the existing literature. Our anticipated results will confirm overestimation of HNO3 formation rate in previous work and provide further constraints on other nitrogen reaction rate coefficients that affect terminal products from NOx. We will particularly focus on organic nitrate chemistry that laboratory literature has yet to fully address. The results will provide useful insights into nitrogen chemistry that affects climate and human health.

D-region ion-neutral coupled chemistry (Sodankylä Ion Chemistry, SIC) within the Whole Atmosphere Community Climate Model (WACCM 4) - WACCM-SIC and WACCM-rSIC

Science.gov (United States)

Kovács, Tamás; Plane, John M. C.; Feng, Wuhu; Nagy, Tibor; Chipperfield, Martyn P.; Verronen, Pekka T.; Andersson, Monika E.; Newnham, David A.; Clilverd, Mark A.; Marsh, Daniel R.

2016-09-01

This study presents a new ion-neutral chemical model coupled into the Whole Atmosphere Community Climate Model (WACCM). The ionospheric D-region (altitudes ˜ 50-90 km) chemistry is based on the Sodankylä Ion Chemistry (SIC) model, a one-dimensional model containing 307 ion-neutral and ion recombination, 16 photodissociation and 7 photoionization reactions of neutral species, positive and negative ions, and electrons. The SIC mechanism was reduced using the simulation error minimization connectivity method (SEM-CM) to produce a reaction scheme of 181 ion-molecule reactions of 181 ion-molecule reactions of 27 positive and 18 negative ions. This scheme describes the concentration profiles at altitudes between 20 km and 120 km of a set of major neutral species (HNO3, O3, H2O2, NO, NO2, HO2, OH, N2O5) and ions (O2+, O4+, NO+, NO+(H2O), O2+(H2O), H+(H2O), H+(H2O)2, H+(H2O)3, H+(H2O)4, O3-, NO2-, O-, O2, OH-, O2-(H2O), O2-(H2O)2, O4-, CO3-, CO3-(H2O), CO4-, HCO3-, NO2-, NO3-, NO3-(H2O), NO3-(H2O)2, NO3-(HNO3), NO3-(HNO3)2, Cl-, ClO-), which agree with the full SIC mechanism within a 5 % tolerance. Four 3-D model simulations were then performed, using the impact of the January 2005 solar proton event (SPE) on D-region HOx and NOx chemistry as a test case of four different model versions: the standard WACCM (no negative ions and a very limited set of positive ions); WACCM-SIC (standard WACCM with the full SIC chemistry of positive and negative ions); WACCM-D (standard WACCM with a heuristic reduction of the SIC chemistry, recently used to examine HNO3 formation following an SPE); and WACCM-rSIC (standard WACCM with a reduction of SIC chemistry using the SEM-CM method). The standard WACCM misses the HNO3 enhancement during the SPE, while the full and reduced model versions predict significant NOx, HOx and HNO3 enhancements in the mesosphere during solar proton events. The SEM-CM reduction also identifies the important ion-molecule reactions that affect the partitioning of

Improving Students' Understanding of Molecular Structure through Broad-Based Use of Computer Models in the Undergraduate Organic Chemistry Lecture

Science.gov (United States)

Springer, Michael T.

2014-01-01

Several articles suggest how to incorporate computer models into the organic chemistry laboratory, but relatively few papers discuss how to incorporate these models broadly into the organic chemistry lecture. Previous research has suggested that "manipulating" physical or computer models enhances student understanding; this study…

Low temperature nitrogen chemistry. Final report

Energy Technology Data Exchange (ETDEWEB)

Glarborg, P.; Dam-Johansen, K.; Kristensen, P.G.; Alzueta, M.; Roejel, H.

1997-04-01

The results of a two tasks program on Natural Gas Reburning are reported. The work involved an experimental and theoretical study of the reburning and hybrid reburning/SNCR chemistry in the 1000-1500 K range. The interactions between hydrocarbon and nitrogen chemistry under fuel-rich conditions were investigated in order to assess the NO{sub x} reduction potential of low temperature reburning. The effect of reburn fuel(carbon monoxide, methane, acetylene, ethylene, ethane, and methane/ethane mixture), temperature, stoichiometry, reactant dilution, reaction time, and inlet NO level were studied. The results indicate a significant NO reduction potential even below 1400 K, but extrapolation to practical conditions are complicated by inadequate knowledge of the detailed chemistry as well as of the effect of mixing. The possibilities of enhancing the conversion to N{sub 2} instead of NO by adding selective reducing agents (hybrid reburning/SNCR) were evaluated. Our results indicate little synergistic effect between reburn and SNCR. The most simple configuration, where the selective reducing agent is injected together with the burnout air, is not expected to be effective, unless the N-agent is injected in form of an aqueous solution. A chemical kinetic model for reburning and reburn/SNCR is listed and can be obtained by e-mail from pgl(commerical at)kt.dtu.dk.(au) 145 refs.

Simulating atmospheric composition over a South-East Asian tropical rainforest: performance of a chemistry box model

Directory of Open Access Journals (Sweden)

T. A. M. Pugh

2010-01-01

Full Text Available Atmospheric composition and chemistry above tropical rainforests is currently not well established, particularly for south-east Asia. In order to examine our understanding of chemical processes in this region, the performance of a box model of atmospheric boundary layer chemistry is tested against measurements made at the top of the rainforest canopy near Danum Valley, Malaysian Borneo. Multi-variate optimisation against ambient concentration measurements was used to estimate average canopy-scale emissions for isoprene, total monoterpenes and nitric oxide. The excellent agreement between estimated values and measured fluxes of isoprene and total monoterpenes provides confidence in the overall modelling strategy, and suggests that this method may be applied where measured fluxes are not available, assuming that the local chemistry and mixing are adequately understood. The largest contributors to the optimisation cost function at the point of best-fit are OH (29%, NO (22% and total peroxy radicals (27%. Several factors affect the modelled VOC chemistry. In particular concentrations of methacrolein (MACR and methyl-vinyl ketone (MVK are substantially overestimated, and the hydroxyl radical (OH concentration is substantially underestimated; as has been seen before in tropical rainforest studies. It is shown that inclusion of dry deposition of MACR and MVK and wet deposition of species with high Henry's Law values substantially improves the fit of these oxidised species, whilst also substantially decreasing the OH sink. Increasing OH production arbitrarily, through a simple OH recycling mechanism , adversely affects the model fit for volatile organic compounds (VOCs. Given the constraints on isoprene flux provided by measurements, a substantial decrease in the rate of reaction of VOCs with OH is the only remaining option to explain the measurement/model discrepancy for OH. A reduction in the isoprene+OH rate constant of 50%, in conjunction with

Ions in solution basic principles of chemical interactions

CERN Document Server

Burgess, J

1999-01-01

This outline of the principles and chemical interactions in inorganic solution chemistry delivers a course module in an area of considerable complexity. Problems with solutions and tutorial hints to test comprehension have been added as a feature to check readers' understanding and assist self-study. Exercises and projects are also provided to help readers deepen and extend their knowledge and understanding. Inorganic solution chemistry is treated thoroughly Emphasis is placed upon NMR, UV-VIS, IR Raman spectroscopy, X-ray diffraction, and such topics as acid-base behaviour, stability constants and kinetics.

Coarse-Grained Modeling of Polyelectrolyte Solutions

Science.gov (United States)

Denton, Alan R.; May, Sylvio

2014-03-01

Ionic mixtures, such as electrolyte and polyelectrolyte solutions, have attracted much attention recently for their rich and challenging combination of electrostatic and non-electrostatic interparticle forces and their practical importance, from battery technologies to biological systems. Hydration of ions in aqueous solutions is known to entail ion-specific effects, including variable solubility of organic molecules, as manifested in the classic Hofmeister series for salting-in and salting-out of proteins. The physical mechanism by which the solvent (water) mediates effective interactions between ions, however, is still poorly understood. Starting from a microscopic model of a polyelectrolyte solution, we apply a perturbation theory to derive a coarse-grained model of ions interacting through both long-range electrostatic and short-range solvent-induced pair potentials. Taking these effective interactions as input to molecular dynamics simulations, we calculate structural and thermodynamic properties of aqueous ionic solutions. This work was supported by the National Science Foundation under Grant No. DMR-1106331.

A context based approach using Green Chemistry/Bio-remediation principles to enhance interest and learning of organic chemistry in a high school AP chemistry classroom

Science.gov (United States)

Miller, Tricia

The ability of our planet to sustain life and heal itself is not as predictable as it used to be. Our need for educated future scientists who know what our planet needs, and can passionately apply that knowledge to find solutions should be at the heart of science education today. This study of learning organic chemistry through the lens of the environmental problem "What should be done with our food scraps?" explores student interest, and mastery of certain concepts in organic chemistry. This Green Chemistry/ Bio-remediation context-based teaching approach utilizes the Nature MillRTM, which is an indoor food waste composting machine, to learn about organic chemistry, and how this relates to landfill reduction possibilities, and resource production. During this unit students collected food waste from their cafeteria, and used the Nature MillRTM to convert food waste into compost. The use of these hands on activities, and group discussions in a context-based environment enhanced their interest in organic chemistry, and paper chromatography. According to a one-tailed paired T-test, the result show that this context-based approach is a significant way to increase both student interest and mastery of the content.

Coupling between water chemistry and thermal output at unsaturated repositories

International Nuclear Information System (INIS)

Walton, J.; LeMone, D.; Casey, D.

1995-01-01

This paper summarizes issues in predicting thermohydrology in the near field of a deep geological repository and the implications for performance assessment. Predicted thermohydrology depends on waste package design, and particularly on backfill materials. The coupling between solute concentrations and thermal gradients leads to a prediction of highly variable water chemistry in the near field which is radically different than the initial, undisturbed water chemistry; however, most analyses to date assume that waste package chemistry is approximately the same as initial pore water chemistry. Several alternative, simplified approaches for performance assessment are discussed

Chemistry Division. Quarterly progress report for period ending June 30, 1949

Energy Technology Data Exchange (ETDEWEB)

1949-09-14

Progress reports are presented for the following tasks: (1) nuclear and chemical properties of heavy elements (solution chemistry, phase rule studies); (2) nuclear and chemical properties of elements in the fission product region; (3) general nuclear chemistry; (4) radio-organic chemistry; (5) chemistry of separations processes; (6) physical chemistry and chemical physics; (7) radiation chemistry; (8) physical measurements and instrumentation; and (9) analytical chemistry. The program of the chemistry division is divided into two efforts of approximately equal weight with respect to number of personnel, chemical research, and analytical service for the Laboratory. The various research problems fall into the following classifications: (1) chemical separation processes for isolation and recovery of fissionable material, production of radioisotopes, and military applications; (2) reactor development; and (3) fundamental research.

Forefront of PUREX system engineering. Chemistry and engineering of ruthenium, technetium and neptunium

International Nuclear Information System (INIS)

2004-07-01

The paper reports the activity of the research committee organized by the Atomic Energy Society of Japan on 'Ruthenium and Technetium Chemistry in the PUREX System', with focusing on basic behaviors of ruthenium, technetium and neptunium in the PUREX process, the principles of plant design, and behaviors during the final waste treatment. The scope of the work includes the following major topics: (1) basic solution and solid-state chemistry; (2) basic solution and solid-state chemistry of minor actinides in particular, Np; (3) partitioning chemistry in the PUREX system and environmental behavior of the components; (4) processes of recovery, purification, and utilization of rare metal fission products; (5) field data on plant design, operation, decontamination, and decommissioning; (6) numerical process simulations and process control technologies; (7) compilation of a data base for process chemistry and plant engineering. (S. Ohno)

Dynamics of forest soil chemistry

Energy Technology Data Exchange (ETDEWEB)

Alveteg, M

1998-11-01

Acidification caused by emissions of nitrogen and sulphur and associated adverse effects on forest ecosystems has been an issue on the political agenda for decades. Temporal aspects of soil acidification and/or recovery can be investigated using the soil chemistry model SAFE, a dynamic version of the steady-state model PROFILE used in critical loads assessment on the national level, e.g. for Sweden. In this thesis, possibilities to replace the use of apparent gibbsite solubility coefficients with a more mechanistic Al sub-model are investigated and a reconstruction model, MAKEDEP, is presented which makes hindcasts and forecasts of atmospheric deposition and nutrient uptake and cycling. A regional application of SAFE/MAKEDEP based on 622 sites in Switzerland is also presented. It is concluded that the quantitative information on pools and fluxes of Al in forest ecosystems is very limited and that there currently exists no mechanistic alternative in modelling soil solution Al. MAKEDEP is a valuable and operational tool for deriving input to dynamic soil chemistry models such as SMART, MAGIC and SAFE. For multi-layer models, e.g. the SAFE model, including nutrient cycling in MAKEDEP is shown to be important. The strength of the regional assessment strategy presented in this thesis lies in its transparency and modularity. All sub-modules, including models, transfer functions, assumptions in the data acquisition strategy, etc., can be checked and replaced individually. As the presented assessment strategy is based on knowledge and data from a wide range of scientists and fields it is of vital importance that the research community challenge the assumptions made. The many measurable intermediate results produced by the included models will hopefully encourage scientists to challenge the models through additional measurements at the calculation sites. It is concluded that current reduction plans are not sufficient for all forest ecosystems in Switzerland to recover from

Variability in chemistry of surface and soil waters of an ...

African Journals Online (AJOL)

Water chemistry is important for the maintenance of wetland structure and function. Interpreting ecological patterns in a wetland system therefore requires an in-depth understanding of the water chemistry of that system. We investigated the spatial distribution of chemical solutes both in soil pore water and surface water, ...

Use of pulse radiolysis for the study of the chemistry of aqueous ozone and ozonide solutions

DEFF Research Database (Denmark)

Sehested, Knud; Holcman, Jerzy; Bjergbakke, Erling

1986-01-01

The chemistry of aqeous ozone, O3, and ozonide, O3−, is of great interest from a technological, environmental and scientific point of view. The literature about their aqueous chemistry is extensive, the reaction mechanisms are still not well understood. The ozonide anion is a free radical that is...... reactions and provides kinetic data sufficient for computer simulations of aqueous O3/O3− chemistry.......The chemistry of aqeous ozone, O3, and ozonide, O3−, is of great interest from a technological, environmental and scientific point of view. The literature about their aqueous chemistry is extensive, the reaction mechanisms are still not well understood. The ozonide anion is a free radical...

Radiation chemistry in solvent extraction: FY2010 Research

International Nuclear Information System (INIS)

Mincher, Bruce J.; Martin, Leigh R.; Mezyk, Stephen P.

2010-01-01

This report summarizes work accomplished under the Fuel Cycle Research and Development (FCR and D) program in the area of radiation chemistry during FY 2010. The tasks assigned during FY 2010 included: (1) Development of techniques to measure free radical reaction kinetics in the organic phase. (2) Initiation of an alpha-radiolysis program; (3) Initiation of an effort to understand dose rate effects in radiation chemistry; (4) Continued work to characterize TALSPEAK radiation chemistry Progress made on each of these tasks is reported here. Briefly, a method was developed and used to measure the kinetics of the reactions of the NO3 radical with solvent extraction ligands in organic solution, and the method to measure OH radical reactions under the same conditions has been designed. Rate constants for the CMPO and DMDOHEMA reaction with NO3 radical in organic solution are reported. Alpha-radiolysis was initiated on samples of DMDOHEMA in alkane solution using He ion beam irradiation and 211At isotope irradiation. The samples are currently being analyzed for comparison to DMDOHEMA ?-irradiations using a custom-developed mass spectrometric method. Results are also reported for the radiolytic generation of nitrous acid, in ?-irradiated nitric acid. It is shown that the yield of nitrous acid is unaffected by an order-of-magnitude change in dose rate. Finally, recent results for TALSPEAK radiolysis are reported, summarizing the effects on solvent extraction efficiency due to HDEHP irradiation, and the stable products of lactic acid and DTPA irradiation. In addition, results representing increased scope are presented for the radiation chemistry program. These include an investigation of the effect of metal complexation on radical reaction kinetics using DTPA as an example, and the production of a manuscript reporting the mechanism of Cs-7SB radiolysis. The Cs-7SB work takes advantage of recent results from a current LDRD program to understand the fundamental chemistry of

The quantum Rabi model: solution and dynamics

International Nuclear Information System (INIS)

Xie, Qiongtao; Zhong, Honghua; Lee, Chaohong; Batchelor, Murray T

2017-01-01

This article presents a review of recent developments on various aspects of the quantum Rabi model. Particular emphasis is given on the exact analytic solution obtained in terms of confluent Heun functions. The analytic solutions for various generalisations of the quantum Rabi model are also discussed. Results are also reviewed on the level statistics and the dynamics of the quantum Rabi model. The article concludes with an introductory overview of several experimental realisations of the quantum Rabi model. An outlook towards future developments is also given. (topical review)

Assessment of a sequential extraction protocol by examining solution chemistry and mineralogical evolution

Science.gov (United States)

Maubec, Nicolas; Pauwels, Hélène; Noël, Hervé; Bourrat, Xavier

2015-04-01

séquentielles et spéciation des éléments trace métalliques dans les sols naturels. Analyse critique. 7, 179-189. Das, A. K., Chakraborty, R., Cervera, M. L., and Delaguardia, M. (1995). Metal speciation in solid matrices. Talanta, 42. Gomez Ariza, J. L., Giraldez, I., Sanchez-Rodas, D., and Morales, E. (2000). Selectivity assessment of a sequential extraction procedure for metal mobility characterization using model phases. Talanta, 52, 545-554. Hickey, M. G., and Kittrick, J. A. (1984). Chemical partitioning of cadmium, copper, nickel and zinc in soils and sediments containing high-levels of heavy metals. Journal of Environmental Quality, 13, 372-376. La Force, M. J., Fendorf, S., Li, G. C., and Rosenzweig, R. F. (1999). Redistribution of trace elements from contaminated sediments of Lake Coeur d'Alene during oxygenation. Journal of Environmental Quality, 28, 1195-1200. Quevauviller, P., Rauret, G., Muntau, H., Ure, A. M., Rubio, R., Lopezsanchez, J. F., Fiedler, H. D., and Griepink, B. (1994). Evaluation of a sequential extraction procedure for the determination of extractable trace-metal contents in sediments. Fresenius Journal of Analytical Chemistry, 349. Rauret, G. (1998). Extraction procedures for the determination of heavy metals in contaminated soil and sediment. Talanta, 46(3), 449-455. Sterckeman, T., Douay, F., Baize, D., Fourrier, H., Proix, N., and Schvartz, C. (2004). Factors affecting trace element concentrations in soils developed on recent marine deposits from northern France. Applied Geochemistry, 19. Tack, F. M. G., and Verloo, M. G. (1995). Chemical speciation and fraéctination in soil and sediment heavy-metal analysis - a review. International Journal of Environmental Analytical Chemistry, 59, 225-238. Tessier, A., Campbell, P. G. C., and Bisson, M. (1979). Sequential extraction procedure for the speciation of particulate trace-metals. Analytical Chemistry, 51. Van Oort, F., Jongmans, A. G., Lamy, I., Baize, D., and Chevallier, P. (2008

Solution Calorimetry Experiments for Physical Chemistry.

Science.gov (United States)

Raizen, Deborah A.; And Others

1988-01-01

Presents two experiments: the first one measures the heat of an exothermic reaction by the reduction of permanganate by the ferris ion; the second one measures the heat of an endothermic process, the mixing of ethanol and cyclohexane. Lists tables to aid in the use of the solution calorimeter. (MVL)

Physical chemistry and the environment

International Nuclear Information System (INIS)

Dunning, T.H. Jr.; Garrett, B.C.; Kolb, C.E. Jr.; Shaw, R.W.; Choppin, G.R.; Wagner, A.F.

1994-08-01

From the ozone hole and the greenhouse effect to plastics recycling and hazardous waste disposal, society faces a number of issues, the solutions to which require an unprecedented understanding of the properties of molecules. We are coming to realize that the environment is a coupled set of chemical systems, its dynamics determining the welfare of the biosphere and of humans in particular. These chemical systems are governed by fundamental molecular interactions, and they present chemists with an unparalleled challenge. The application of current concepts of molecular behavior and of up-to-date experimental and computational techniques can provide us with insights into the environment that are needed to mitigate past damage, to anticipate the impact of current human activity, and to avoid future insults to the environment. Environmental chemistry encompasses a number of separate, yet interlocking, areas of research. In all of these areas progress is limited by an inadequate understanding of the underlying chemical processes involved. Participation of all chemical approaches -- experimental, theoretical and computational -- and of all disciplines of chemistry -- organic, inorganic, physical, analytical and biochemistry -- will be required to provide the necessary fundamental understanding. The Symposium on ''Physical Chemistry and the Environment'' was designed to bring the many exciting and challenging physical chemistry problems involved in environmental chemistry to the attention of a larger segment of the physical chemistry community

Predicting steam generator crevice chemistry

International Nuclear Information System (INIS)

Burton, G.; Strati, G.

2006-01-01

'Full text:' Corrosion of steam cycle components produces insoluble material, mostly iron oxides, that are transported to the steam generator (SG) via the feedwater and deposited on internal surfaces such as the tubes, tube support plates and the tubesheet. The build up of these corrosion products over time can lead to regions of restricted flow with water chemistry that may be significantly different, and potentially more corrosive to SG tube material, than the bulk steam generator water chemistry. The aim of the present work is to predict SG crevice chemistry using experimentation and modelling as part of AECL's overall strategy for steam generator life management. Hideout-return experiments are performed under CANDU steam generator conditions to assess the accumulation of impurities in hideout, and return from, model crevices. The results are used to validate the ChemSolv model that predicts steam generator crevice impurity concentrations, and high temperature pH, based on process parameters (e.g., heat flux, primary side temperature) and blowdown water chemistry. The model has been incorporated into ChemAND, AECL's system health monitoring software for chemistry monitoring, analysis and diagnostics that has been installed at two domestic and one international CANDU station. ChemAND provides the station chemists with the only method to predict SG crevice chemistry. In one recent application, the software has been used to evaluate the crevice chemistry based on the elevated, but balanced, SG bulk water impurity concentrations present during reactor startup, in order to reduce hold times. The present paper will describe recent hideout-return experiments that are used for the validation of the ChemSolv model, station experience using the software, and improvements to predict the crevice electrochemical potential that will permit station staff to ensure that the SG tubes are in the 'safe operating zone' predicted by Lu (AECL). (author)

Parameterization of dust emissions in the global atmospheric chemistry-climate model EMAC: impact of nudging and soil properties

OpenAIRE

Astitha, M.; Lelieveld, J.; Kader, M. Abdel; Pozzer, A.; de Meij, A.

2012-01-01

Airborne desert dust influences radiative transfer, atmospheric chemistry and dynamics, as well as nutrient transport and deposition. It directly and indirectly affects climate on regional and global scales. Two versions of a parameterization scheme to compute desert dust emissions are incorporated into the atmospheric chemistry general circulation model EMAC (ECHAM5/MESSy2.41 Atmospheric Chemistry). One uses a global...

Flowfield and Radiation Analysis of Missile Exhaust Plumes Using a Turbulent-Chemistry Interaction Model

National Research Council Canada - National Science Library

Calhoon, W. H; Kenzakowski, D. C

2000-01-01

... components and missile defense systems. Current engineering level models neglect turbulent-chemistry interactions and typically underpredict the intensity of plume afterburning and afterburning burnout...

Progress report 1981-1982. Reactor Chemistry Department

International Nuclear Information System (INIS)

1983-08-01

Review of the activities performed by the Reactor Chemistry Department of the National Atomic Energy Commission of Argentina during 1981-1982. This Department provides services and assistance in all matters related to water chemistry and nuclear reactors chemistry, in all their phases: design, construction, commissioning and decommissioning. During this period, the following tasks were performed: study of the metallic oxide-water interphases; determination of the goethite and magnetite surficial charges; synthesis of the monodispersed nickel ferrites; study of the iron oxides dissolution mechanism in presence of different complexing agents; chemical decontamination of structural metals; thermodynamics of the water-nitrogen system; physico-chemical studies of aqueous solutions at high temperatures; hydrothermal decomposition of ionic exchange resines and study of the equilibria of the anionic exchange for the chemistry of pressurized reactor's primary loops. The appendix includes information on the Reactor Chemistry Department staff, its publications, services, seminars, courses and conferences performed during 1981-1982. (R.J.S.) [es

Effect of surface chemistry, solution pH, and ionic strength on the removal of herbicides diuron and amitrole from water by an activated carbon fiber.

Science.gov (United States)

Fontecha-Cámara, M A; López-Ramón, M V; Alvarez-Merino, M A; Moreno-Castilla, C

2007-01-30

A study was conducted on the effects of carbon surface chemistry, solution pH, and ionic strength on the removal of diuron and amitrole from aqueous solutions by adsorption on an as-received and oxidized activated carbon fiber. Results obtained were explained by the surface characteristics of the adsorbents and the characteristics of the herbicide molecules. Under the experimental conditions used, diuron uptake was much higher than that of amitrole, despite its larger molecular dimensions, due to the lesser water solubility, greater hydrophobicity, and larger dipolar moment of diuron compared with amitrole. Uptake variations associated with differences in carbon surface oxidation, solution pH, and ionic strength were explained by corresponding changes in electrostatic, hydrophobic, and van der Waals interactions.

Modeling of the chemistry in oxidation flow reactors with high initial NO

Science.gov (United States)

Peng, Zhe; Jimenez, Jose L.

2017-10-01

Oxidation flow reactors (OFRs) are increasingly employed in atmospheric chemistry research because of their high efficiency of OH radical production from low-pressure Hg lamp emissions at both 185 and 254 nm (OFR185) or 254 nm only (OFR254). OFRs have been thought to be limited to studying low-NO chemistry (in which peroxy radicals (RO2) react preferentially with HO2) because NO is very rapidly oxidized by the high concentrations of O3, HO2, and OH in OFRs. However, many groups are performing experiments by aging combustion exhaust with high NO levels or adding NO in the hopes of simulating high-NO chemistry (in which RO2 + NO dominates). This work systematically explores the chemistry in OFRs with high initial NO. Using box modeling, we investigate the interconversion of N-containing species and the uncertainties due to kinetic parameters. Simple initial injection of NO in OFR185 can result in more RO2 reacted with NO than with HO2 and minor non-tropospheric photolysis, but only under a very narrow set of conditions (high water mixing ratio, low UV intensity, low external OH reactivity (OHRext), and initial NO concentration (NOin) of tens to hundreds of ppb) that account for a very small fraction of the input parameter space. These conditions are generally far away from experimental conditions of published OFR studies with high initial NO. In particular, studies of aerosol formation from vehicle emissions in OFRs often used OHRext and NOin several orders of magnitude higher. Due to extremely high OHRext and NOin, some studies may have resulted in substantial non-tropospheric photolysis, strong delay to RO2 chemistry due to peroxynitrate formation, VOC reactions with NO3 dominating over those with OH, and faster reactions of OH-aromatic adducts with NO2 than those with O2, all of which are irrelevant to ambient VOC photooxidation chemistry. Some of the negative effects are the worst for alkene and aromatic precursors. To avoid undesired chemistry, vehicle emissions

Segment-based Eyring-Wilson viscosity model for polymer solutions

International Nuclear Information System (INIS)

Sadeghi, Rahmat

2005-01-01

A theory-based model is presented for correlating viscosity of polymer solutions and is based on the segment-based Eyring mixture viscosity model as well as the segment-based Wilson model for describing deviations from ideality. The model has been applied to several polymer solutions and the results show that it is reliable both for correlation and prediction of the viscosity of polymer solutions at different molar masses and temperature of the polymer

The Breath of Chemistry

DEFF Research Database (Denmark)

Josephsen, Jens

The present preliminary text is a short thematic presentation in biological inorganic chemistry meant to illustrate general and inorganic (especially coordination) chemistry in biochemistry. The emphasis is on molecular models to explain features of the complicated mechanisms essential to breathing...

Visualizing Chemistry: Investigations for Teachers.

Science.gov (United States)

Ealy, Julie B.; Ealy, James L., Jr.

This book contains 101 investigations for chemistry classrooms. Topics include: (1) Physical Properties; (2) Reactions of Some Elements; (3) Reactions Involving Gases; (4) Energy Changes; (5) Solutions and Solubility; (6) Transition Metals and Complex Ions; (7) Kinetics and Equilibrium; (8) Acids and Bases; (9) Oxidation-Reduction; (10)…

Kinetic modeling and simulation of PCE and TCE removal in aqueous solutions by electron-beam irradiation

International Nuclear Information System (INIS)

Nickelsen, Michael G.; Cooper, William J.; Secker, David A.; Rosocha, Louis A.; Kurucz, Charles N.; Waite, Thomas D.

2002-01-01

The irradiation of aqueous solutions of TCE and PCE using a high-energy electron-beam results in the rapid decomposition of both chemicals. It is known that both TCE and PCE react with the aqueous electron and the hydroxyl radical with bimolecular rate constants greater than 10 9 M -1 s -1 for each reaction. The fact that high-energy electrons produce significant concentrations of both e aq - and ·OH radicals in water makes it an effective process for the removal of TCE and PCE from aqueous solution. We have employed steady state and computer-based chemical kinetic models to simulate and better understand the chemistry and kinetics of e-beam irradiation when applied to natural water systems. Model results were benchmarked to experimental data, allowing for the optimization of the reaction of DOC with the ·OH radical. Values for the associated second-order reaction rate constant were found to be 2.5x10 8 and 4.0x10 8 M -1 s -1 , consistent with reported values for k OH,DOC . The models were also used to investigate the possibility of incomplete irradiation during treatment and the presence of proposed chemical reactions of by-products. The reactions involve radicals and radical-adduct species formed by the reaction of TCE and PCE with the hydroxyl radical

Redox Models in Chemistry Textbooks for the Upper Secondary School: Friend or Foe?

Science.gov (United States)

Osterlund, Lise-Lotte; Berg, Anders; Ekborg, Margareta

2010-01-01

We have investigated how chemistry textbooks use models of redox reactions in different subject areas, how they change models between and within the topics, and how they deal with specific learning difficulties identified in the literature. The textbooks examined were published for use in the natural science programme in Swedish upper secondary…

Dimethylsulfide Chemistry: Annual, Seasonal, and Spatial Impacts on Sulfate

Science.gov (United States)

We incorporated oceanic emissions and atmospheric chemistry of dimethylsulfide (DMS) into the hemispheric Community Multiscale Air Quality model and performed annual model simulations without and with DMS chemistry. The model without DMS chemistry predicts higher concentrations o...

Development of collaborative-creative learning model using virtual laboratory media for instrumental analytical chemistry lectures

Science.gov (United States)

Zurweni, Wibawa, Basuki; Erwin, Tuti Nurian

2017-08-01

The framework for teaching and learning in the 21st century was prepared with 4Cs criteria. Learning providing opportunity for the development of students' optimal creative skills is by implementing collaborative learning. Learners are challenged to be able to compete, work independently to bring either individual or group excellence and master the learning material. Virtual laboratory is used for the media of Instrumental Analytical Chemistry (Vis, UV-Vis-AAS etc) lectures through simulations computer application and used as a substitution for the laboratory if the equipment and instruments are not available. This research aims to design and develop collaborative-creative learning model using virtual laboratory media for Instrumental Analytical Chemistry lectures, to know the effectiveness of this design model adapting the Dick & Carey's model and Hannafin & Peck's model. The development steps of this model are: needs analyze, design collaborative-creative learning, virtual laboratory media using macromedia flash, formative evaluation and test of learning model effectiveness. While, the development stages of collaborative-creative learning model are: apperception, exploration, collaboration, creation, evaluation, feedback. Development of collaborative-creative learning model using virtual laboratory media can be used to improve the quality learning in the classroom, overcome the limitation of lab instruments for the real instrumental analysis. Formative test results show that the Collaborative-Creative Learning Model developed meets the requirements. The effectiveness test of students' pretest and posttest proves significant at 95% confidence level, t-test higher than t-table. It can be concluded that this learning model is effective to use for Instrumental Analytical Chemistry lectures.

Development of a Grid-Independent Geos-Chem Chemical Transport Model (v9-02) as an Atmospheric Chemistry Module for Earth System Models

Science.gov (United States)

Long, M. S.; Yantosca, R.; Nielsen, J. E; Keller, C. A.; Da Silva, A.; Sulprizio, M. P.; Pawson, S.; Jacob, D. J.

2015-01-01

The GEOS-Chem global chemical transport model (CTM), used by a large atmospheric chemistry research community, has been re-engineered to also serve as an atmospheric chemistry module for Earth system models (ESMs). This was done using an Earth System Modeling Framework (ESMF) interface that operates independently of the GEOSChem scientific code, permitting the exact same GEOSChem code to be used as an ESM module or as a standalone CTM. In this manner, the continual stream of updates contributed by the CTM user community is automatically passed on to the ESM module, which remains state of science and referenced to the latest version of the standard GEOS-Chem CTM. A major step in this re-engineering was to make GEOS-Chem grid independent, i.e., capable of using any geophysical grid specified at run time. GEOS-Chem data sockets were also created for communication between modules and with external ESM code. The grid-independent, ESMF-compatible GEOS-Chem is now the standard version of the GEOS-Chem CTM. It has been implemented as an atmospheric chemistry module into the NASA GEOS- 5 ESM. The coupled GEOS-5-GEOS-Chem system was tested for scalability and performance with a tropospheric oxidant-aerosol simulation (120 coupled species, 66 transported tracers) using 48-240 cores and message-passing interface (MPI) distributed-memory parallelization. Numerical experiments demonstrate that the GEOS-Chem chemistry module scales efficiently for the number of cores tested, with no degradation as the number of cores increases. Although inclusion of atmospheric chemistry in ESMs is computationally expensive, the excellent scalability of the chemistry module means that the relative cost goes down with increasing number of cores in a massively parallel environment.

The aqueous chemistry of oxides

CERN Document Server

Bunker, Bruce C

2016-01-01

The Aqueous Chemistry of Oxides is a comprehensive reference volume and special topics textbook that explores all of the major chemical reactions that take place between oxides and aqueous solutions. The book highlights the enormous impact that oxide-water reactions have in advanced technologies, materials science, geochemistry, and environmental science.

Radioanalytical Chemistry for Automated Nuclear Waste Process Monitoring

International Nuclear Information System (INIS)

Egorov, Oleg B.; Grate, Jay W.; DeVol, Timothy A.

2004-01-01

This research program is directed toward rapid, sensitive, and selective determination of beta and alpha-emitting radionuclides such as 99Tc, 90Sr, and trans-uranium (TRU) elements in low activity waste (LAW) processing streams. The overall technical approach is based on automated radiochemical measurement principles, which entails integration of sample treatment and separation chemistries and radiometric detection within a single functional analytical instrument. Nuclear waste process streams are particularly challenging for rapid analytical methods due to the complex, high-ionic-strength, caustic brine sample matrix, the presence of interfering radionuclides, and the variable and uncertain speciation of the radionuclides of interest. As a result, matrix modification, speciation control, and separation chemistries are required for use in automated process analyzers. Significant knowledge gaps exist relative to the design of chemistries for such analyzers so that radionuclides can be quantitatively and rapidly separated and analyzed in solutions derived from low-activity waste processing operations. This research is addressing these knowledge gaps in the area of separation science, nuclear detection, and analytical chemistry and instrumentation. The outcome of these investigations will be the knowledge necessary to choose appropriate chemistries for sample matrix modification and analyte speciation control and chemistries for rapid and selective separation and preconcentration of target radionuclides from complex sample matrices. In addition, new approaches for quantification of alpha emitters in solution using solid-state diode detectors, as well as improved instrumentation and signal processing techniques for use with solid-state and scintillation detectors, will be developed. New knowledge of the performance of separation materials, matrix modification and speciation control chemistries, instrument configurations, and quantitative analytical approaches will

Effects of atmospheric deposition nitrogen flux and its composition on soil solution chemistry from a red soil farmland, southeast China.

Science.gov (United States)

Cui, Jian; Zhou, Jing; Peng, Ying; Chan, Andrew; Mao, Jingdong

2015-12-01

A detailed study on the solution chemistry of red soil in South China is presented. Data are collected from two simulated column-leaching experiments with an improved setup to evaluate the effects of atmospheric N deposition (ADN) composition and ADN flux on agricultural soil acidification using a (15)N tracer technique and an in situ soil solution sampler. The results show that solution pH values decline regardless of the increase of the NH4(+)/NO3(-) ratio in the ADN composition or ADN flux, while exchangeable Al(3+), Ca(2+), Mg(2+), and K(+) concentrations increase at different soil depths (20, 40, and 60 cm). Compared with the control, ADN (60 kg per ha per year N, NH4(+)/NO3(-) ratio of 2 : 1) decreases solution pH values, increases solution concentrations of NO3(-)-N, Al(3+), Ca(2+) and Mg(2+) at the middle and lower soil depths, and promotes their removal. NH4(+)-N was not detected in red soil solutions of all the three soil layers, which might be attributed to effects of nitrification, absorption and fixation in farmland red soil. Some of the NO3(-)-N concentrations at 40-60 cm soil depth exceed the safe drinking level of 10 mg L(-1), especially when the ADN flux is beyond 60 kg ha(-1) N. These features are critical for understanding the ADN agro-ecological effects, and for future assessment of ecological critical loads of ADN in red soil farmlands.

Chemistry resolved kinetic flow modeling of TATB based explosives

Science.gov (United States)

Vitello, Peter; Fried, Laurence E.; William, Howard; Levesque, George; Souers, P. Clark

2012-03-01

Detonation waves in insensitive, TATB-based explosives are believed to have multiple time scale regimes. The initial burn rate of such explosives has a sub-microsecond time scale. However, significant late-time slow release in energy is believed to occur due to diffusion limited growth of carbon. In the intermediate time scale concentrations of product species likely change from being in equilibrium to being kinetic rate controlled. We use the thermo-chemical code CHEETAH linked to an ALE hydrodynamics code to model detonations. We term our model chemistry resolved kinetic flow, since CHEETAH tracks the time dependent concentrations of individual species in the detonation wave and calculates EOS values based on the concentrations. We present here two variants of our new rate model and comparison with hot, ambient, and cold experimental data for PBX 9502.

Multivariate Calibration and Model Integrity for Wood Chemistry Using Fourier Transform Infrared Spectroscopy

Directory of Open Access Journals (Sweden)

Chengfeng Zhou

2015-01-01

Full Text Available This research addressed a rapid method to monitor hardwood chemical composition by applying Fourier transform infrared (FT-IR spectroscopy, with particular interest in model performance for interpretation and prediction. Partial least squares (PLS and principal components regression (PCR were chosen as the primary models for comparison. Standard laboratory chemistry methods were employed on a mixed genus/species hardwood sample set to collect the original data. PLS was found to provide better predictive capability while PCR exhibited a more precise estimate of loading peaks and suggests that PCR is better for model interpretation of key underlying functional groups. Specifically, when PCR was utilized, an error in peak loading of ±15 cm−1 from the true mean was quantified. Application of the first derivative appeared to assist in improving both PCR and PLS loading precision. Research results identified the wavenumbers important in the prediction of extractives, lignin, cellulose, and hemicellulose and further demonstrated the utility in FT-IR for rapid monitoring of wood chemistry.

Periodic solutions of nonautonomous differential systems modeling obesity population

International Nuclear Information System (INIS)

Arenas, Abraham J.; Gonzalez-Parra, Gilberto; Jodar, Lucas

2009-01-01

In this paper we study the periodic behaviour of the solutions of a nonautonomous model for obesity population. The mathematical model represented by a nonautonomous system of nonlinear ordinary differential equations is used to model the dynamics of obese populations. Numerical simulations suggest periodic behaviour of subpopulations solutions. Sufficient conditions which guarantee the existence of a periodic positive solution are obtained using a continuation theorem based on coincidence degree theory.

Periodic solutions of nonautonomous differential systems modeling obesity population

Energy Technology Data Exchange (ETDEWEB)

Arenas, Abraham J. [Departamento de Matematicas y Estadistica, Universidad de Cordoba Monteria (Colombia)], E-mail: aarenas@sinu.unicordoba.edu.co; Gonzalez-Parra, Gilberto [Departamento de Calculo, Universidad de los Andes, Merida (Venezuela, Bolivarian Republic of)], E-mail: gcarlos@ula.ve; Jodar, Lucas [Instituto de Matematica Multidisciplinar, Universidad Politecnica de Valencia Edificio 8G, 2o, 46022 Valencia (Spain)], E-mail: ljodar@imm.upv.es

2009-10-30

In this paper we study the periodic behaviour of the solutions of a nonautonomous model for obesity population. The mathematical model represented by a nonautonomous system of nonlinear ordinary differential equations is used to model the dynamics of obese populations. Numerical simulations suggest periodic behaviour of subpopulations solutions. Sufficient conditions which guarantee the existence of a periodic positive solution are obtained using a continuation theorem based on coincidence degree theory.

The secret to successful solute-transport modeling

Science.gov (United States)

Konikow, Leonard F.

2011-01-01

Modeling subsurface solute transport is difficult—more so than modeling heads and flows. The classical governing equation does not always adequately represent what we see at the field scale. In such cases, commonly used numerical models are solving the wrong equation. Also, the transport equation is hyperbolic where advection is dominant, and parabolic where hydrodynamic dispersion is dominant. No single numerical method works well for all conditions, and for any given complex field problem, where seepage velocity is highly variable, no one method will be optimal everywhere. Although we normally expect a numerically accurate solution to the governing groundwater-flow equation, errors in concentrations from numerical dispersion and/or oscillations may be large in some cases. The accuracy and efficiency of the numerical solution to the solute-transport equation are more sensitive to the numerical method chosen than for typical groundwater-flow problems. However, numerical errors can be kept within acceptable limits if sufficient computational effort is expended. But impractically long

Recollections of the maturation of radiation chemistry

International Nuclear Information System (INIS)

Dainton, F.S.

1989-01-01

In this paper the background to the study of the identification of primary species in irradiated aqueous solutions is presented. Theoretical aspects are discussed. The radiation chemistry of glossy and crystalline solids is briefly discussed. (UK)

A Comprehensive General Chemistry Demonstration

Science.gov (United States)

Sweeder, Ryan D.; Jeffery, Kathleen A.

2013-01-01

This article describes the use of a comprehensive demonstration suitable for a high school or first-year undergraduate introductory chemistry class. The demonstration involves placing a burning candle in a container adjacent to a beaker containing a basic solution with indicator. After adding a lid, the candle will extinguish and the produced…

IN-PACKAGE CHEMISTRY ABSTRACTION

Energy Technology Data Exchange (ETDEWEB)

E. Thomas

2005-07-14

This report was developed in accordance with the requirements in ''Technical Work Plan for Postclosure Waste Form Modeling'' (BSC 2005 [DIRS 173246]). The purpose of the in-package chemistry model is to predict the bulk chemistry inside of a breached waste package and to provide simplified expressions of that chemistry as a function of time after breach to Total Systems Performance Assessment for the License Application (TSPA-LA). The scope of this report is to describe the development and validation of the in-package chemistry model. The in-package model is a combination of two models, a batch reactor model, which uses the EQ3/6 geochemistry-modeling tool, and a surface complexation model, which is applied to the results of the batch reactor model. The batch reactor model considers chemical interactions of water with the waste package materials, and the waste form for commercial spent nuclear fuel (CSNF) waste packages and codisposed (CDSP) waste packages containing high-level waste glass (HLWG) and DOE spent fuel. The surface complexation model includes the impact of fluid-surface interactions (i.e., surface complexation) on the resulting fluid composition. The model examines two types of water influx: (1) the condensation of water vapor diffusing into the waste package, and (2) seepage water entering the waste package as a liquid from the drift. (1) Vapor-Influx Case: The condensation of vapor onto the waste package internals is simulated as pure H{sub 2}O and enters at a rate determined by the water vapor pressure for representative temperature and relative humidity conditions. (2) Liquid-Influx Case: The water entering a waste package from the drift is simulated as typical groundwater and enters at a rate determined by the amount of seepage available to flow through openings in a breached waste package.

IN-PACKAGE CHEMISTRY ABSTRACTION

International Nuclear Information System (INIS)

E. Thomas

2005-01-01

This report was developed in accordance with the requirements in ''Technical Work Plan for Postclosure Waste Form Modeling'' (BSC 2005 [DIRS 173246]). The purpose of the in-package chemistry model is to predict the bulk chemistry inside of a breached waste package and to provide simplified expressions of that chemistry as a function of time after breach to Total Systems Performance Assessment for the License Application (TSPA-LA). The scope of this report is to describe the development and validation of the in-package chemistry model. The in-package model is a combination of two models, a batch reactor model, which uses the EQ3/6 geochemistry-modeling tool, and a surface complexation model, which is applied to the results of the batch reactor model. The batch reactor model considers chemical interactions of water with the waste package materials, and the waste form for commercial spent nuclear fuel (CSNF) waste packages and codisposed (CDSP) waste packages containing high-level waste glass (HLWG) and DOE spent fuel. The surface complexation model includes the impact of fluid-surface interactions (i.e., surface complexation) on the resulting fluid composition. The model examines two types of water influx: (1) the condensation of water vapor diffusing into the waste package, and (2) seepage water entering the waste package as a liquid from the drift. (1) Vapor-Influx Case: The condensation of vapor onto the waste package internals is simulated as pure H 2 O and enters at a rate determined by the water vapor pressure for representative temperature and relative humidity conditions. (2) Liquid-Influx Case: The water entering a waste package from the drift is simulated as typical groundwater and enters at a rate determined by the amount of seepage available to flow through openings in a breached waste package

The chemical bond in inorganic chemistry the bond valence model

CERN Document Server

Brown, I David

2016-01-01

The bond valence model is a version of the ionic model in which the chemical constraints are expressed in terms of localized chemical bonds formed by the valence charge of the atoms. Theorems derived from the properties of the electrostatic flux predict the rules obeyed by both ionic and covalent bonds. They make quantitative predictions of coordination number, crystal structure, bond lengths and bond angles. Bond stability depends on the matching of the bonding strengths of the atoms, while the conflicting requirements of chemistry and space lead to the structural instabilities responsible for the unusual physical properties displayed by some materials. The model has applications in many fields ranging from mineralogy to molecular biology.

Planetary Sources for Reducing Sulfur Compounds for Cyanosulfidic Origins of Life Chemistry

Science.gov (United States)

Ranjan, S.; Todd, Z. R.; Sutherland, J.; Sasselov, D. D.

2017-12-01

A key challenge in origin-of-life studies is understanding the chemistry that lead to the origin of the key biomolecules of life, such as the components of nucleic acids, sugars, lipids, and proteins. Prebiotic reaction networks based upon reductive homologation of nitriles (e.g., Patel et al. 2015), are building a tantalizing picture of sustained abiotic synthesis of activated ribonucleotides, amino acids and lipid precursors under environmental conditions thought to have been available on early Earth. Sulfidic anions in aqueous solution (e.g., HS-, HSO3-) under near-UV irradiation play important roles in these chemical pathways. However, the sources and availability of these anions on early Earth have not yet been quantitatively constrained. Here, we evaluate the potential for the atmosphere to serve as a source of sulfidic anions, via dissolution of volcanically-outgassed SO2 and H2S into water reservoirs. We combine photochemical modeling from the literature (Hu et al. 2013) with equilibrium chemistry calculations to place constraints on the partial pressures of SO2 and H2S required to reach the elevated concentrations of sulfidic anions (≥1 μM) thought to be necessary for prebiotic chemistry. We find that micromolar levels of SO2-derived anions (HSO3-, SO3(2-)) are possible through simple exposure of aqueous reservoirs like shallow lakes to the atmosphere, assuming total sulfur emission flux comparable to today. Millimolar levels of these compounds are available during the epochs of elevated volcanism, due to elevated sulfur emission flux. Radiative transfer modeling suggests the atmospheric sulfur will not block the near-UV radiation also required for the cyanosulfidic chemistry. However, H2S-derived anions (e.g., HS-) reach only sub-micromolar levels from atmospheric sources, meaning that prebiotic chemistry invoking such molecules must invoke specialized, local sources. Prebiotic chemistry invoking SO2-derived anions may be considered more robust than

Radioanalytical Chemistry for Automated Nuclear Waste Process Monitoring

International Nuclear Information System (INIS)

Egorov, Oleg B.; Grate, Jay W.; DeVol, Timothy A.

2003-01-01

This research program is directed toward rapid, sensitive, and selective determination of beta and alpha-emitting radionuclides such as 99Tc, 90Sr, and trans-uranium (TRU) elements in low activity waste (LAW) processing streams. The overall technical approach is based on automated radiochemical measurement principles. Nuclear waste process streams are particularly challenging for rapid analytical methods due to the complex, high- ionic-strength, caustic brine sample matrix, the presence of interfering radionuclides, and the variable and uncertain speciation of the radionuclides of interest. As a result, matrix modification, speciation control, and separation chemistries are required for use in automated process analyzers. Significant knowledge gaps exist relative to the design of chemistries for such analyzers so that radionuclides can be quantitatively and rapidly separated and analyzed in solutions derived from low-activity waste processing operations. This research is addressing these knowledge gaps in the area of separation science, nuclear detection, and analytical chemistry and instrumentation. The outcome of these investigations will be the knowledge necessary to choose appropriate chemistries for sample matrix modification and analyte speciation control and chemistries for rapid and selective separation and preconcentration of target radionuclides from complex sample matrices. In addition, new approaches for quantification of alpha emitters in solution using solid state diode detectors, as well as improved instrumentation and signal processing techniques for use with solid-state and scintillation detectors, will be developed. New knowledge of the performance of separation materials, matrix modification and speciation control chemistries, instrument configurations, and quantitative analytical approaches will provide the basis for designing effective instrumentation for radioanalytical process monitoring. Specific analytical targets include 99 Tc, 90Sr and

Mathematical modeling of solute transport in the subsurface

International Nuclear Information System (INIS)

Naymik, T.G.

1987-01-01

A review of key works on solute transport models indicates that solute transport processes with the exception of advection are still poorly understood. Solute transport models generally do a good job when they are used to test scientific concepts and hypotheses, investigate natural processes, systematically store and manage data, and simulate mass balance of solutes under certain natural conditions. Solute transport models generally are not good for predicting future conditions with a high degree of certainty, or for determining concentrations precisely. The mathematical treatment of solute transport far surpasses their understanding of the process. Investigations of the extent of groundwater contamination and methods to remedy existing problems show the along-term nature of the hazard. Industrial organic compounds may be immiscible in water, highly volatile, or complexed with inorganic as well as other organic compounds; many remain stable in nature almost indefinitely. In the worst case, future disposal of hazardous waste may be restricted to deep burial, as is proposed for radioactive wastes. For investigations pertinent to transport of radionuclides from a geologic repository, the process cannot be fully understood without adequate thermodynamic and kinetic data bases

Modeling Chemistry for Effective Chemical Education: An Interview with Ronald J. Gillespie

Science.gov (United States)

Cardellini, Liberato

2010-01-01

Ronald J. Gillespie, the inventor of the Valence Shell Electron Pair Repulsion (VSEPR) model, relates how his career as researcher in Christopher Ingold's laboratories started. Gillespie developed a passion for chemistry and chemical education, searching for more appropriate and interesting ways to transmit the essential knowledge and enthusiasm…

Kiche: A simulation tool for kinetics of iodine chemistry in the containment of light water reactors under severe accident conditions (Contract research)

International Nuclear Information System (INIS)

Moriyama, Kiyofumi; Maruyama, Yu; Nakamura, Hideo

2011-03-01

An iodine chemistry simulation tool, Kiche, was developed for analyses of chemical kinetics relevant to iodine volatilization in the containment vessel of light water reactors (LWRs) during a severe accident. It consists of a Fortran code to solve chemical kinetics models, reaction databases written in plain text format, and peripheral tools to convert the reaction databases into Fortran codes to solve corresponding ordinary differential equation sets. Potential advantages of Kiche are the text format reaction database separated from the code that provides flexibility of the chemistry model, and, being a Fortran code which is relatively easily coupled with other Fortran codes such as severe accident analysis codes. This document describes the model, solution method, code structure, and examples of application of Kiche for simulation of experiments. The calculation results by the present model agreed well with the experimental data and it indicates the model properly includes the most important processes in the volatilization of iodine from irradiated iodide solutions with or without organic impurities. The appendixes give practical information for the usage of Kiche. (author)

Recirculating cooling water solute depletion models

International Nuclear Information System (INIS)

Price, W.T.

1990-01-01

Chromates have been used for years to inhibit copper corrosion in the plant Recirculating Cooling Water (RCW) system. However, chromates have become an environmental problem in recent years both in the chromate removal plant (X-616) operation and from cooling tower drift. In response to this concern, PORTS is replacing chromates with Betz Dianodic II, a combination of phosphates, BZT, and a dispersant. This changeover started with the X-326 system in 1989. In order to control chemical concentrations in X-326 and in systems linked to it, we needed to be able to predict solute concentrations in advance of the changeover. Failure to predict and control these concentrations can result in wasted chemicals, equipment fouling, or increased corrosion. Consequently, Systems Analysis developed two solute concentration models. The first simulation represents the X-326 RCW system by itself; and models the depletion of a solute once the feed has stopped. The second simulation represents the X-326, X-330, and the X-333 systems linked together by blowdown. This second simulation represents the concentration of a solute in all three systems simultaneously. 4 figs

Chemistry and biology by new multiple choice

International Nuclear Information System (INIS)

Seo, Hyeong Seok; Kim, Seong Hwan

2003-02-01

This book is divided into two parts, the first part is about chemistry, which deals with science of material, atom structure and periodic law, chemical combination and power between molecule, state of material and solution, chemical reaction and an organic compound. The second part give description of biology with molecule and cell, energy in cells and chemical synthesis, molecular biology and heredity, function on animal, function on plant and evolution and ecology. This book has explanation of chemistry and biology with new multiple choice.

Hydrolysis and Radiation Chemistry of the DGAs

Energy Technology Data Exchange (ETDEWEB)

Mincher, Bruce Jay [Idaho National Lab. (INL), Idaho Falls, ID (United States); Zarzana, Christopher Andrew [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2016-09-01

This document was prepared to meet FCR&D level 3 milestone M3FT-16IN030104052, “continue the study of the short chain compounds,” and, “ study the radiolysis of the non-symmetrical DGA (D3DODGA)….,” under the Radiation Chemistry FCR&D work package. Toward these goals, the short chain DGA, tetraethyldiglycolamide (TEDGA) was investigated for its hydrolytic stability in HNO3 solution, with comparisons to the less oxidizing mineral acid HCl. Initial gamma-irradiations were also performed on DGA solutions, to inform a more detailed investigation of several short chain compounds anticipated for FY17. The hydrolytic and radiolysis behavior of TEDGA is of interest for two reasons. First, previous long chain DGA radiolysis was conducted in dodecane solution since the long chain compounds are soluble in that diluent, and new radiation chemistry is expected in the aqueous environment due to reactions with •OH radical. The second reason is that this water-soluble DGA has been proposed for use as a stripping or holdback agent in both European and American fuel cycle scenarios. Therefore, this work was performed in collaboration Forschungszentrum Jülich (FZJ), and the European SACSESS program. Additionally, results are presented here regarding the radiation of chemistry the non-symmetrical DGA didodecyldioctyldiglycolamide (D3DODGA), for comparison to previous work with symmetrical DGAs such as TODGA and TEHDGA. This was also conducted in collaboration with researchers in the SACSESS program.

In-Package Chemistry Abstraction

Energy Technology Data Exchange (ETDEWEB)

E. Thomas

2004-11-09

This report was developed in accordance with the requirements in ''Technical Work Plan for: Regulatory Integration Modeling and Analysis of the Waste Form and Waste Package'' (BSC 2004 [DIRS 171583]). The purpose of the in-package chemistry model is to predict the bulk chemistry inside of a breached waste package and to provide simplified expressions of that chemistry as function of time after breach to Total Systems Performance Assessment for the License Application (TSPA-LA). The scope of this report is to describe the development and validation of the in-package chemistry model. The in-package model is a combination of two models, a batch reactor model that uses the EQ3/6 geochemistry-modeling tool, and a surface complexation model that is applied to the results of the batch reactor model. The batch reactor model considers chemical interactions of water with the waste package materials and the waste form for commercial spent nuclear fuel (CSNF) waste packages and codisposed waste packages that contain both high-level waste glass (HLWG) and DOE spent fuel. The surface complexation model includes the impact of fluid-surface interactions (i.e., surface complexation) on the resulting fluid composition. The model examines two types of water influx: (1) the condensation of water vapor that diffuses into the waste package, and (2) seepage water that enters the waste package from the drift as a liquid. (1) Vapor Influx Case: The condensation of vapor onto the waste package internals is simulated as pure H2O and enters at a rate determined by the water vapor pressure for representative temperature and relative humidity conditions. (2) Water Influx Case: The water entering a waste package from the drift is simulated as typical groundwater and enters at a rate determined by the amount of seepage available to flow through openings in a breached waste package. TSPA-LA uses the vapor influx case for the nominal scenario for simulations where the waste

In-Package Chemistry Abstraction

International Nuclear Information System (INIS)

E. Thomas

2004-01-01

This report was developed in accordance with the requirements in ''Technical Work Plan for: Regulatory Integration Modeling and Analysis of the Waste Form and Waste Package'' (BSC 2004 [DIRS 171583]). The purpose of the in-package chemistry model is to predict the bulk chemistry inside of a breached waste package and to provide simplified expressions of that chemistry as function of time after breach to Total Systems Performance Assessment for the License Application (TSPA-LA). The scope of this report is to describe the development and validation of the in-package chemistry model. The in-package model is a combination of two models, a batch reactor model that uses the EQ3/6 geochemistry-modeling tool, and a surface complexation model that is applied to the results of the batch reactor model. The batch reactor model considers chemical interactions of water with the waste package materials and the waste form for commercial spent nuclear fuel (CSNF) waste packages and codisposed waste packages that contain both high-level waste glass (HLWG) and DOE spent fuel. The surface complexation model includes the impact of fluid-surface interactions (i.e., surface complexation) on the resulting fluid composition. The model examines two types of water influx: (1) the condensation of water vapor that diffuses into the waste package, and (2) seepage water that enters the waste package from the drift as a liquid. (1) Vapor Influx Case: The condensation of vapor onto the waste package internals is simulated as pure H2O and enters at a rate determined by the water vapor pressure for representative temperature and relative humidity conditions. (2) Water Influx Case: The water entering a waste package from the drift is simulated as typical groundwater and enters at a rate determined by the amount of seepage available to flow through openings in a breached waste package. TSPA-LA uses the vapor influx case for the nominal scenario for simulations where the waste package has been

Development of solute transport models in YMPYRÄ framework to simulate solute migration in military shooting and training areas

Science.gov (United States)

Warsta, L.; Karvonen, T.

2017-12-01

There are currently 25 shooting and training areas in Finland managed by The Finnish Defence Forces (FDF), where military activities can cause contamination of open waters and groundwater reservoirs. In the YMPYRÄ project, a computer software framework is being developed that combines existing open environmental data and proprietary information collected by FDF with computational models to investigate current and prevent future environmental problems. A data centric philosophy is followed in the development of the system, i.e. the models are updated and extended to handle available data from different areas. The results generated by the models are summarized as easily understandable flow and risk maps that can be opened in GIS programs and used in environmental assessments by experts. Substances investigated with the system include explosives and metals such as lead, and both surface and groundwater dominated areas can be simulated. The YMPYRÄ framework is composed of a three dimensional soil and groundwater flow model, several solute transport models and an uncertainty assessment system. Solute transport models in the framework include particle based, stream tube and finite volume based approaches. The models can be used to simulate solute dissolution from source area, transport in the unsaturated layers to groundwater and finally migration in groundwater to water extraction wells and springs. The models can be used to simulate advection, dispersion, equilibrium adsorption on soil particles, solubility and dissolution from solute phase and dendritic solute decay chains. Correct numerical solutions were confirmed by comparing results to analytical 1D and 2D solutions and by comparing the numerical solutions to each other. The particle based and stream tube type solute transport models were useful as they could complement the traditional finite volume based approach which in certain circumstances produced numerical dispersion due to piecewise solution of the

The Learner Characteristics, Features of Desktop 3D Virtual Reality Environments, and College Chemistry Instruction: A Structural Equation Modeling Analysis

Science.gov (United States)

Merchant, Zahira; Goetz, Ernest T.; Keeney-Kennicutt, Wendy; Kwok, Oi-man; Cifuentes, Lauren; Davis, Trina J.

2012-01-01

We examined a model of the impact of a 3D desktop virtual reality environment on the learner characteristics (i.e. perceptual and psychological variables) that can enhance chemistry-related learning achievements in an introductory college chemistry class. The relationships between the 3D virtual reality features and the chemistry learning test as…

Predicting tropospheric ozone and hydroxyl radical in a global, three-dimensional, chemistry, transport, and deposition model

Energy Technology Data Exchange (ETDEWEB)

Atherton, C.S.

1995-01-05

Two of the most important chemically reactive tropospheric gases are ozone (O{sub 3}) and the hydroxyl radical (OH). Although ozone in the stratosphere is a necessary protector against the sun`s radiation, tropospheric ozone is actually a pollutant which damages materials and vegetation, acts as a respiratory irritant, and is a greenhouse gas. One of the two main sources of ozone in the troposphere is photochemical production. The photochemistry is initiated when hydrocarbons and carbon monoxide (CO) react with nitrogen oxides (NO{sub x} = NO + NO{sub 2}) in the presence of sunlight. Reaction with the hydroxyl radical, OH, is the main sink for many tropospheric gases. The hydroxyl radical is highly reactive and has a lifetime on the order of seconds. Its formation is initiated by the photolysis of tropospheric ozone. Tropospheric chemistry involves a complex, non-linear set of chemical reactions between atmospheric species that vary substantially in time and space. To model these and other species on a global scale requires the use of a global, three-dimensional chemistry, transport, and deposition (CTD) model. In this work, I developed two such three dimensional CTD models. The first model incorporated the chemistry necessary to model tropospheric ozone production from the reactions of nitrogen oxides with carbon monoxide (CO) and methane (CH{sub 4}). The second also included longer-lived alkane species and the biogenic hydrocarbon isoprene, which is emitted by growing plants and trees. The models` ability to predict a number of key variables (including the concentration of O{sub 3}, OH, and other species) were evaluated. Then, several scenarios were simulated to understand the change in the chemistry of the troposphere since preindustrial times and the role of anthropogenic NO{sub x} on present day conditions.

The Solution Construction of Heterotic Super-Liouville Model

Science.gov (United States)

Yang, Zhan-Ying; Zhen, Yi

2001-12-01

We investigate the heterotic super-Liouville model on the base of the basic Lie super-algebra Osp(1|2).Using the super extension of Leznov-Saveliev analysis and Drinfeld-Sokolov linear system, we construct the explicit solution of the heterotic super-Liouville system in component form. We also show that the solutions are local and periodic by calculating the exchange relation of the solution. Finally starting from the action of heterotic super-Liouville model, we obtain the conserved current and conserved charge which possessed the BRST properties.

Water and Aqueous Solutions: Simple Non-Speculative Model Approach

Czech Academy of Sciences Publication Activity Database

Nezbeda, Ivo; Jirsák, Jan

2011-01-01

Roč. 13, č. 44 (2011), s. 19689-19703 ISSN 1463-9076 R&D Projects: GA AV ČR IAA400720802; GA AV ČR IAA200760905 Institutional research plan: CEZ:AV0Z40720504 Keywords : molecular modeling of water * separation * perturbation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.573, year: 2011

A molecular-thermodynamic model for polyelectrolyte solutions

Energy Technology Data Exchange (ETDEWEB)

Jiang, J.; Liu, H.; Hu, Y. [Thermodynamics Research Laboratory, East China University of Science and Technology, Shanghai 200237 (China); Prausnitz, J.M. [Department of Chemical Engineering, University of California, Berkeley, and Chemical Sciences Division, Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720 (United States)

1998-01-01

Polyelectrolyte solutions are modeled as freely tangent-jointed, charged hard-sphere chains and corresponding counterions in a continuum medium with permitivity {var_epsilon}. By adopting the sticky-point model, the Helmholtz function for polyelectrolyte solutions is derived through the r-particle cavity-correlation function (CCF) for chains of sticky, charged hard spheres. The r-CCF is approximated by a product of effective nearest-neighbor two-particle CCFs; these are determined from the hypernetted-chain and mean-spherical closures (HNC/MSA) inside and outside the hard core, respectively, for the integral equation theory for electrolytes. The colligative properties are given as explicit functions of a scaling parameter {Gamma} that can be estimated by a simple iteration procedure. Osmotic pressures, osmotic coefficients, and activity coefficients are calculated for model solutions with various chain lengths. They are in good agreement with molecular simulation and experimental results. {copyright} {ital 1998 American Institute of Physics.}

Radiation chemistry in solvent extraction: FY2010 Research

Energy Technology Data Exchange (ETDEWEB)

Bruce J. Mincher; Leigh R. Martin; Stephen P. Mezyk

2010-09-01

This report summarizes work accomplished under the Fuel Cycle Research and Development (FCR&D) program in the area of radiation chemistry during FY 2010. The tasks assigned during FY 2010 included: • Development of techniques to measure free radical reaction kinetics in the organic phase. • Initiation of an alpha-radiolysis program • Initiation of an effort to understand dose rate effects in radiation chemistry • Continued work to characterize TALSPEAK radiation chemistry Progress made on each of these tasks is reported here. Briefly, a method was developed and used to measure the kinetics of the reactions of the •NO3 radical with solvent extraction ligands in organic solution, and the method to measure •OH radical reactions under the same conditions has been designed. Rate constants for the CMPO and DMDOHEMA reaction with •NO3 radical in organic solution are reported. Alpha-radiolysis was initiated on samples of DMDOHEMA in alkane solution using He ion beam irradiation and 211At isotope irradiation. The samples are currently being analyzed for comparison to DMDOHEMA ?-irradiations using a custom-developed mass spectrometric method. Results are also reported for the radiolytic generation of nitrous acid, in ?-irradiated nitric acid. It is shown that the yield of nitrous acid is unaffected by an order-of-magnitude change in dose rate. Finally, recent results for TALSPEAK radiolysis are reported, summarizing the effects on solvent extraction efficiency due to HDEHP irradiation, and the stable products of lactic acid and DTPA irradiation. In addition, results representing increased scope are presented for the radiation chemistry program. These include an investigation of the effect of metal complexation on radical reaction kinetics using DTPA as an example, and the production of a manuscript reporting the mechanism of Cs-7SB radiolysis. The Cs-7SB work takes advantage of recent results from a current LDRD program to understand the fundamental chemistry

Chemistry for the nuclear energy of the future

International Nuclear Information System (INIS)

Chmielewski, A.G.

2011-01-01

Chemistry - radiochemistry, radiation chemistry and nuclear chemical engineering play a very important role in the nuclear power development. Even at present, the offered technology is well developed, but still several improvements are needed and proposed. These developments concern all stages of the technology; front end, reactor operation (coolant chemistry and installation components decontamination, noble gas release control), back end of fuel cycle, etc. Chemistry for a partitioning and a transmutation is a new challenge for the chemists and chemical engineers. The IV th generation of nuclear reactors cannot be developed without chemical solutions for fuel fabrication, radiation-coolants interaction phenomena understanding and spent fuel/waste treatment technologies elaboration. Radiochemical analytical methods are fundamental for radioecological monitoring of radioisotopes of natural and anthropological origin. This paper addresses just a few subjects and is not a detailed overview of the field, however it illustrates a role of chemistry for a safe and economical nuclear power development. (author)

Determination of Quantum Chemistry Based Force Fields for Molecular Dynamics Simulations of Aromatic Polymers

Science.gov (United States)

Jaffe, Richard; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

Ab initio quantum chemistry calculations for model molecules can be used to parameterize force fields for molecular dynamics simulations of polymers. Emphasis in our research group is on using quantum chemistry-based force fields for molecular dynamics simulations of organic polymers in the melt and glassy states, but the methodology is applicable to simulations of small molecules, multicomponent systems and solutions. Special attention is paid to deriving reliable descriptions of the non-bonded and electrostatic interactions. Several procedures have been developed for deriving and calibrating these parameters. Our force fields for aromatic polyimide simulations will be described. In this application, the intermolecular interactions are the critical factor in determining many properties of the polymer (including its color).

A Performance Enhanced Interactive Learning Workshop Model as a Supplement for Organic Chemistry Instruction

Science.gov (United States)

Phillips, Karen E. S.; Grose-Fifer, Jilliam

2011-01-01

In this study, the authors describe a Performance Enhanced Interactive Learning (PEIL) workshop model as a supplement for organic chemistry instruction. This workshop model differs from many others in that it includes public presentations by students and other whole-class-discussion components that have not been thoroughly investigated in the…

An Integrated Visualization and Basic Molecular Modeling Laboratory for First-Year Undergraduate Medicinal Chemistry

Science.gov (United States)

Hayes, Joseph M.

2014-01-01

A 3D model visualization and basic molecular modeling laboratory suitable for first-year undergraduates studying introductory medicinal chemistry is presented. The 2 h practical is embedded within a series of lectures on drug design, target-drug interactions, enzymes, receptors, nucleic acids, and basic pharmacokinetics. Serving as a teaching aid…

Stochastic dynamics modeling solute transport in porous media modeling solute transport in porous media

CERN Document Server

Kulasiri, Don

2002-01-01

Most of the natural and biological phenomena such as solute transport in porous media exhibit variability which can not be modeled by using deterministic approaches. There is evidence in natural phenomena to suggest that some of the observations can not be explained by using the models which give deterministic solutions. Stochastic processes have a rich repository of objects which can be used to express the randomness inherent in the system and the evolution of the system over time. The attractiveness of the stochastic differential equations (SDE) and stochastic partial differential equations (SPDE) come from the fact that we can integrate the variability of the system along with the scientific knowledge pertaining to the system. One of the aims of this book is to explaim some useufl concepts in stochastic dynamics so that the scientists and engineers with a background in undergraduate differential calculus could appreciate the applicability and appropriateness of these developments in mathematics. The ideas ...

NATO Advanced Research Workshop on The Chemistry of Weathering

CERN Document Server

1985-01-01

Several important developments in our understanding of the chemistry of weathering have occurred in the last few years: 1. There has been a major breakthrough in our understanding of the mechanisms controlling the kinetics of sil icate dissolution, and there have been major advances in computer modeling of weathering processes. 2. There has been a growing recognition of the importance of organic solutes in the weathering process, and hence of the inter-relationships between mineral weathering and the terrestrial ecosystem. 3. The impact of acid deposition ("acid rain") has been widely recognized. The processes by which acid deposition is neutral ized are closely related to the processes of normal chemical weathering; an understanding of the chemistry of weathering is thus essential for predicting the effects of acid deposition. 4. More high-qual ity data have become available on the chemical dynamics of smal I watersheds and large river systems, which represent the integrated effects of chemical weathering.

Present status of water chemistry in nuclear power plants

International Nuclear Information System (INIS)

Berge, Ph.; Fiquet, J.M.

1991-01-01

As operational experience increases, solutions to mitigate corrosion problems of existing plants are found. They also, hopefully, can solve the corrosion problems for future reactors when materials and design can be modified. Improvement of chemistry solved numerous early problems in PWRs (denting, pitting) and limitated other phenomena such as erosion-corrosion of steels in the secondary circuit. Chemistry has not been successful for other problems such as primary-side cracking of PWRs and has been moderately efficient for stress corrosion cracking or IGA of tubes at the support plate. Based on the experience, several recommendations for an optimum chemistry can be formulated. (author)

Abstracts Book of 3. All-Polish Conference on Radiochemistry and Nuclear Chemistry

International Nuclear Information System (INIS)

2001-01-01

The development of radiochemistry and nuclear chemistry in Poland have been presented during the 3. All-Polish Conference on Radiochemistry and Nuclear Chemistry held in Kazimierz Dolny in May 2001. The broad range of problems connected with radiochemistry and nuclear chemistry application in environmental protection and quality control, nuclear medicine and radiation protection, radioactive waste processing and many other scientific and everyday problems solution have been extensively presented and discussed

Computer analysis of potentiometric data of complexes formation in the solution

Science.gov (United States)

Jastrzab, Renata; Kaczmarek, Małgorzata T.; Tylkowski, Bartosz; Odani, Akira

2018-02-01

The determination of equilibrium constants is an important process for many branches of chemistry. In this review we provide the readers with a discussion on computer methods which have been applied for elaboration of potentiometric experimental data generated during complexes formation in solution. The review describes both: general basis of modeling tools and examples of the use of calculated stability constants.

Mid-year report: IPC liaison and chemistry of thermal reconstitution

International Nuclear Information System (INIS)

Delegard, C.H.

1995-05-01

A program of investigation into the chemistry of alkaline Hanford Site tank waste is being conducted. The investigations have two main subtasks: liaison with the Institute of Physical Chemistry of the Russian Academy of Sciences and further laboratory testing of the chemistry of thermal reconstitution of Hanford Site tank waste. Progress to date includes: (1) a technical dialogue has been established with the Institute scientists; (2) editing of a technical literature review on the chemistry of the transuranic elements and technetium in alkaline media written by researchers at the Institute is complete; (3) four tasks from the Institute have been selected for support by the US Department of Energy; (4) technical information has been supplied to the Institute describing the composition of Hanford Site tank waste; (5) tests, using genuine waste from tank 104-S (a REDOX Process sludge), comparing the performance of thermal reconstitution with enhanced sludge washing show markedly improved dissolution of aluminum achieved by the thermal treatment; (6) a reduction/coprecipitation method was tested and shown to remove plutonium, solubilized by thermal treatment, rapidly and efficiently from solution; (7) technical chemistry support was provided to calciner kinetics tests at the University of Idaho; (8) tests to determine the speciation of plutonium and neptunium solubilized by thermal treatment show dissolved Pu(V) and Np(V) hydroxide complexes are produced, a Np(V) peroxide complex also was identified; (9) recently published data on Pu(IV) carbonate complexation in moderately alkaline (pH 12 to 13) solution led to reexamination of previous investigations of plutonium complexation in highly alkaline (3 to 5 molar NaOH) solutions

A Generalized Deduction of the Ideal-Solution Model

Science.gov (United States)

Leo, Teresa J.; Perez-del-Notario, Pedro; Raso, Miguel A.

2006-01-01

A new general procedure for deriving the Gibbs energy of mixing is developed through general thermodynamic considerations, and the ideal-solution model is obtained as a special particular case of the general one. The deduction of the Gibbs energy of mixing for the ideal-solution model is a rational one and viewed suitable for advanced students who…

Chemistry and radiation in oxy-fuel combustion

DEFF Research Database (Denmark)

Yin, Chungen; Rosendahl, Lasse; Kær, Søren Knudsen

2011-01-01

In order to investigate the role of combustion chemistry and radiation heat transfer in oxy-fuel combustion modeling, a computational fluid dynamics (CFD) modeling study has been performed for two different oxy-fuel furnaces. One is a lab-scale 0.8MW oxy-natural gas flame furnace whose detailed in....... Among the key issues in combustion modeling, e.g., mixing, radiation and chemistry, this paper derives useful guidelines on radiation and chemistry implementation for reliable CFD analyses of oxy-fuel combustion, particularly for industrial applications....

Geochemical modelling baseline compositions of groundwater

DEFF Research Database (Denmark)

Postma, Diederik Jan; Kjøller, Claus; Andersen, Martin Søgaard

2008-01-01

and variations in water chemistry that are caused by large scale geochemical processes taking place at the timescale of thousands of years. The most important geochemical processes are ion exchange (Valreas and Aveiro) where freshwater solutes are displacing marine ions from the sediment surface, and carbonate......Reactive transport models, were developed to explore the evolution in groundwater chemistry along the flow path in three aquifers; the Triassic East Midland aquifer (UK), the Miocene aquifer at Valreas (F) and the Cretaceous aquifer near Aveiro (P). All three aquifers contain very old groundwaters...... dissolution (East Midlands, Valreas and Aveiro). Reactive transport models, employing the code PHREEQC, which included these geochemical processes and one-dimensional solute transport were able to duplicate the observed patterns in water quality. These models may provide a quantitative understanding...

Modeling of gas-phase chemistry in the chemical vapor deposition of polysilicon in a cold wall system

Energy Technology Data Exchange (ETDEWEB)

Toprac, A.J.; Edgar, T.F.; Trachtenberg, I. (Univ. of Texas, Austin, TX (United States). Dept. of Chemical Engineering)

1993-06-01

The relative contribution of gas-phase chemistry to deposition processes is an important issue both from the standpoint of operation and modeling of these processes. In polysilicon deposition from thermally activated silane in a cold wall rapid thermal chemical vapor deposition (RTCVD) system, the relative contribution of gas-phase chemistry to the overall deposition rate was examined by a mass-balance model. Evaluating the process at conditions examined experimentally, the model indicated that gas-phase reactions may be neglected to good accuracy in predicting polysilicon deposition rate. The model also provided estimates of the level of gas-phase generated SiH[sub 2] associated with deposition on the cold-process chamber walls.

A model study of the plasma chemistry of stratospheric Blue Jets

Science.gov (United States)

Winkler, Holger; Notholt, Justus

2015-04-01

Stratospheric Blue Jets (BJs) are upward propagating discharges in the altitude range 15-40 km above thunderstorms. They appear as conical bodies of blue light originating at the top of thunderclouds and proceed upward with velocities of the order of 100 km/s. Electric discharges in the atmosphere are known to have chemical effects. Of particular interest is the liberation of atomic oxygen and the formation of reactive nitrogen radicals. We have used a numerical plasma chemistry model in order to simulate the chemical processes in stratospheric BJs. It was applied to BJ streamers in the altitude range 18-38 km. The model results show that there is a production of ozone from atomic oxygen liberated at the streamer tips. At the same time, significant amounts of nitric oxide are produced. Compared to earlier plasma chemistry simulations of BJ streamers, the production of NO and O3 is by orders of magnitude larger. Additionally, the chemical processes in the leader part of a BJ have been simulated for the first time. In the leader channel, driven by high-temperature reactions, the concentration of N2O and NO increases by several orders of magnitude, and there is a significant depletion of ozone. The model results might gain importance by the fact that the chemical perturbations in BJs are largest at altitudes of the stratospheric ozone layer.

Expansion of thermodynamic model of solute permeation through reverse osmosis membrane

International Nuclear Information System (INIS)

Nishimaki, Kenzo; Koyama, Akio

1994-01-01

Many studies have been performed on permeation mechanism of solute and solvent in membrane separation process like reverse osmosis or ultrafiltration, and several models of solute/solvent permeation through membrane are proposed. Among these models, Kedem and Katchalsky, based on the theory of thermodynamics of irreversible processes, formulated the one-solute permeation process in their mathematical model, which treats membrane as a black box, not giving consideration to membrane structure and to interaction between membrane material and permeates, viz. solute and solvent. According to this theory, the driving force of solute/solvent permeation through membrane is the difference of their chemical potential between both sides of membrane, and the linear phenomenological equation is applied to describing the relation between driving force and flux of solute/solvent. This equation can be applied to the irreversible process only when the process is almost in equilibrium. This condition is supposed to be satisfied in the solute/solvent permeation process through compact membrane with fine pores like reverse osmosis membrane. When reverse osmosis is applied to treatment process for liquid waste, which usually contains a lot of solutes as contaminants, we can not predict the behavior of contaminants by the above one-solute process model. In the case of multi-solutes permeation process for liquid waste, the number of parameter in thermodynamic model increases rapidly with the number of solute, because of coupling phenomenon among solutes. In this study, we expanded the above thermodynamic model to multi-solute process applying operational calculus to the differential equations which describe the irreversible process of the system, and expressed concisely solute concentration vector as a matrix product. In this way, we predict the behavior of solutes in multi-solutes process, using values of parameters obtained in two-solutes process. (author)

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry.

Science.gov (United States)

Cremer, Paul S; Flood, Amar H; Gibb, Bruce C; Mobley, David L

2017-12-19

On planet Earth, water is everywhere: the majority of the surface is covered with it; it is a key component of all life; its vapour and droplets fill the lower atmosphere; and even rocks contain it and undergo geomorphological changes because of it. A community of physical scientists largely drives studies of the chemistry of water and aqueous solutions, with expertise in biochemistry, spectroscopy and computer modelling. More recently, however, supramolecular chemists - with their expertise in macrocyclic synthesis and measuring supramolecular interactions - have renewed their interest in water-mediated non-covalent interactions. These two groups offer complementary expertise that, if harnessed, offer to accelerate our understanding of aqueous supramolecular chemistry and water writ large. This Review summarizes the state-of-the-art of the two fields, and highlights where there is latent chemical space for collaborative exploration by the two groups.

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

Science.gov (United States)

Cremer, Paul S.; Flood, Amar H.; Gibb, Bruce C.; Mobley, David L.

2018-01-01

On planet Earth, water is everywhere: the majority of the surface is covered with it; it is a key component of all life; its vapour and droplets fill the lower atmosphere; and even rocks contain it and undergo geomorphological changes because of it. A community of physical scientists largely drives studies of the chemistry of water and aqueous solutions, with expertise in biochemistry, spectroscopy and computer modelling. More recently, however, supramolecular chemists -- with their expertise in macrocyclic synthesis and measuring supramolecular interactions -- have renewed their interest in water-mediated non-covalent interactions. These two groups offer complementary expertise that, if harnessed, offer to accelerate our understanding of aqueous supramolecular chemistry and water writ large. This Review summarizes the state-of-the-art of the two fields, and highlights where there is latent chemical space for collaborative exploration by the two groups.

A framework for expanding aqueous chemistry in the Community Multiscale Air Quality (CMAQ) model version 5.1

Science.gov (United States)

Fahey, Kathleen M.; Carlton, Annmarie G.; Pye, Havala O. T.; Baek, Jaemeen; Hutzell, William T.; Stanier, Charles O.; Baker, Kirk R.; Wyat Appel, K.; Jaoui, Mohammed; Offenberg, John H.

2017-04-01

This paper describes the development and implementation of an extendable aqueous-phase chemistry option (AQCHEM - KMT(I)) for the Community Multiscale Air Quality (CMAQ) modeling system, version 5.1. Here, the Kinetic PreProcessor (KPP), version 2.2.3, is used to generate a Rosenbrock solver (Rodas3) to integrate the stiff system of ordinary differential equations (ODEs) that describe the mass transfer, chemical kinetics, and scavenging processes of CMAQ clouds. CMAQ's standard cloud chemistry module (AQCHEM) is structurally limited to the treatment of a simple chemical mechanism. This work advances our ability to test and implement more sophisticated aqueous chemical mechanisms in CMAQ and further investigate the impacts of microphysical parameters on cloud chemistry. Box model cloud chemistry simulations were performed to choose efficient solver and tolerance settings, evaluate the implementation of the KPP solver, and assess the direct impacts of alternative solver and kinetic mass transfer on predicted concentrations for a range of scenarios. Month-long CMAQ simulations for winter and summer periods over the US reveal the changes in model predictions due to these cloud module updates within the full chemical transport model. While monthly average CMAQ predictions are not drastically altered between AQCHEM and AQCHEM - KMT, hourly concentration differences can be significant. With added in-cloud secondary organic aerosol (SOA) formation from biogenic epoxides (AQCHEM - KMTI), normalized mean error and bias statistics are slightly improved for 2-methyltetrols and 2-methylglyceric acid at the Research Triangle Park measurement site in North Carolina during the Southern Oxidant and Aerosol Study (SOAS) period. The added in-cloud chemistry leads to a monthly average increase of 11-18 % in cloud SOA at the surface in the eastern United States for June 2013.

Regularity of solutions of a phase field model

KAUST Repository

Amler, Thomas

2013-01-01

Phase field models are widely-used for modelling phase transition processes such as solidification, freezing or CO2 sequestration. In this paper, a phase field model proposed by G. Caginalp is considered. The existence and uniqueness of solutions are proved in the case of nonsmooth initial data. Continuity of solutions with respect to time is established. In particular, it is shown that the governing initial boundary value problem can be considered as a dynamical system. © 2013 International Press.

Progress report 1985-1986 Reactor Chemistry Department

International Nuclear Information System (INIS)

1987-12-01

The report of the activities performed by the Reactor Chemistry Department of the National Atomic Energy Commission, during the period 1985-1986, covers works of investigation, development and service related to the Argentine Nuclear Power Plants. The main subjects are the experimental and theoretical studies about physical chemistry and chemistry control at the moderators and heat transport system of the nuclear power plants. The more relevant topics are related to: 1: Behaviour of gases, electrolites and other additives for nuclear power plants, at high temperature and pressure; 2: Ionic exchangers of nuclear degree; 3: Electrochemistry studies connected with the constitutive materials' corrosion and with the nuclear power plants decontamination processes; 4: Behaviour of suspensions and colloids in nuclear power plants; 5: Use of new additives for chemistry control of the oxides which are in the circuits of nuclear power plants; 6: Research methods that allow to check reactor's control quality; 7: Study of the radiolytic behaviour of nuclear reactor's solutions. (M.E.L.) [es

Effect of surface chemistries and characteristics of Ti6Al4V on the Ca and P adsorption and ion dissolution in Hank's ethylene diamine tetra-acetic acid solution.

Science.gov (United States)

Chang, E; Lee, T M

2002-07-01

This study examined the influence of chemistries and surface characteristics of Ti6Al4V on the adsorption of Ca and P species and ion dissolution behavior of the material exposed in Hank's solution with 8.0 mM ethylene diamine tetra-acetic acid at 37 degrees C. The variation of chemistries of the alloy and nano-surface characteristics (chemistries of nano-surface oxides, amphoteric OH group adsorbed on oxides, and oxide thickness) was effected by surface modification and three passivation methods (34% nitric acid passivation. 400 degrees C heated in air, and aged in 100 degrees C water). X-ray photoelectron spectroscopy and Auger electron spectroscopy were used for surface analyses. The chemistries of nano-surface oxides in a range studied should not change the capability of Ca and P adsorption. Nor is the capability affected significantly by amphoteric OH group and oxide thickness. However, passivations influence the surface oxide thickness and the early stage ion dissolution rate of the alloy. The rate-limiting step of the rate can be best explained by metal-ion transport through the oxide film, rather than hydrolysis of the film. Variation of the chemistries of titanium alloy alters the electromotive force potential of the metal, thereby affecting the corrosion and ion dissolution rate.

The Titan Haze Simulation Experiment: Latest Laboratory Results and Dedicated Plasma Chemistry Model

Science.gov (United States)

Sciamma-O'Brien, Ella; Raymond, Alexander; Mazur, Eric; Salama, Farid

2018-06-01

Here, we present the latest results on the gas and solid phase analyses in the Titan Haze Simulation (THS) experiment. The THS experiment, developed at NASA Ames’ COSmIC facility is a unique experimental platform that allows us to simulate Titan’s complex atmospheric chemistry at Titan-like temperature (200 K) by cooling down N2-CH4-based mixtures in a supersonic expansion before inducing the chemistry by plasma.Gas phase: The residence time of the jet-accelerated gas in the active plasma region is less than 4 µs, which results in a truncated chemistry enabling us to control how far in the chain of reactions the chemistry is processing. By adding heavier molecules in the initial gas mixture, it is then possible to study the first and intermediate steps of Titan’s atmospheric chemistry as well as specific chemical pathways, as demonstrated by mass spectrometry and comparison to Cassini CAPS data [1]. A new model was recently developed to simulate the plasma chemistry in the THS. Calculated mass spectra produced by this model are in good agreement with the experimental THS mass spectra, confirming that the short residence time in the plasma cavity limits the growth of larger species [2].Solid phase: Scanning electron microscopy and infrared spectroscopy have been used to investigate the effect of the initial gas mixture on the morphology of the THS Titan aerosol analogs as well as on the level and nature of the nitrogen incorporation into these aerosols. A comparison to Cassini VIMS observational data has shown that the THS aerosols produced in simpler mixtures, i.e., that contain more nitrogen and where the N-incorporation is in isocyanide-type molecules instead of nitriles, are more representative of Titan’s aerosols [3]. In addition, a new optical constant facility has been developed at NASA Ames that allows us to determine the complex refractive indices of THS Titan aerosol analogs from NIR to FIR (0.76-222 cm-1). The facility and preliminary results

Solutions manual to accompany finite mathematics models and applications

CERN Document Server

Morris, Carla C

2015-01-01

A solutions manual to accompany Finite Mathematics: Models and Applications In order to emphasize the main concepts of each chapter, Finite Mathematics: Models and Applications features plentiful pedagogical elements throughout such as special exercises, end notes, hints, select solutions, biographies of key mathematicians, boxed key principles, a glossary of important terms and topics, and an overview of use of technology. The book encourages the modeling of linear programs and their solutions and uses common computer software programs such as LINDO. In addition to extensive chapters on pr

Classical solutions of some field theoretic models

International Nuclear Information System (INIS)

Zakrzewski, W.J.

1982-01-01

In recent years much attention has been paid to simpler fields theories, so chosen that they possess several properties of nonabelian gauge theories. They preserve the conformal invariance of the action and one can define the topological charge for them. They possess nontrivial solutions to the equations of motion. The perturbation theory based on the fluctuations around each solution is characterized by asymptotic freedom. A model called CP sup(n-1) is presented and some models which are its natural generalizations are discussed. (M.F.W.)

Multi-skyrmion solutions of a sixth order Skyrme model

International Nuclear Information System (INIS)

Floratos, I.

2001-08-01

In this thesis, we study some of the classical properties of an extension of the Skyrme model defined by adding a sixth order derivative term to the Lagrangian. In chapter 1, we review the physical as well as the mathematical motivation behind the study of the Skyrme model and in chapter 2, we give a brief summary of various extended Skyrme models that have been proposed over the last few years. We then define a new sixth order Skyrme model by introducing a dimensionless parameter λ that denotes the mixing between the two higher order terms, the Skyrme term and the sixth order term. In chapter 3 we compute numerically the multi-skyrmion solutions of this extended model and show that they have the same symmetries with the usual skyrmion solutions. In addition, we analyse the dependence of the energy and radius of these classical solutions with respect to the coupling constant λ. We compare our results with experimental data and determine whether this modified model can provide us with better theoretical predictions than the original one. In chapter 4, we use the rational map ansatz, introduced by Houghton, Manton and Sutcliffe, to approximate minimum energy multi-skyrmion solutions with B ≤ 9 of the SU(2) model and with B ≤ 6 of the SU(3) model. We compare our results with the ones obtained numerically and show that the rational map ansatz works just as well for the generalised model as for the pure Skyrme model, at least for B ≤ 5. In chapter 5, we use a generalisation of the rational map ansatz, introduced by loannidou, Piette and Zakrzewski, to construct analytically some topologically non-trivial solutions of the extended model in SU(3). These solutions are spherically symmetric and some of them can be interpreted as bound states of skyrmions. Finally, we use the same ansatz to construct low energy configurations of the SU(N) sixth order Skyrme model. (author)

Modelling of nitric and nitrous acid chemistry for solvent extraction purposes

Energy Technology Data Exchange (ETDEWEB)

McKenzie, H.; McLachlan, F. [National Nuclear Laboratory, Building D5, Culham Science Centre, Abingdon, Oxfordshire, OX14 3DB (United Kingdom); MacDonald-Taylor, J. [National Nuclear Laboratory, 5th Floor, Chadwick House, Warrington Road, Birchwood Park, Warrington, WA3 6AE (United Kingdom); Orr, R.; Woodhead, D. [National Nuclear Laboratory, Central Laboratory, Sellafield, Seascale, Cumbria, CA20 1PG (United Kingdom)

2016-07-01

Nitric acid plays an integral role in the reprocessing of irradiated fuel. It is well known that nitric acid degrades; its often yellow hue signifies the presence of decomposition products. The decomposition of nitric acid is accelerated by temperature and radiolysis; therefore it is an important consideration in the reprocessing of nuclear fuels. Thermal and radiolytic reactions of nitric acid result in the formation of redox active nitrogen species, of which nitrous acid is of particular concern, largely due to its redox reactions with plutonium and neptunium. Such reactions are important to understand as plutonium and neptunium can exist in a number of oxidation states; the oxidation state has a direct effect on the species extractability. The effect of nitrous acid is exacerbated as it catalyzes its own production and its reactions with actinides are typically autocatalytic; thus even micromolar quantities can have a large effect. A full understanding of solvent extraction requires us to understand actinide valence states which in turn require us to understand what nitrogen species are present and their concentrations. As a first step in the overall objective of enhancing process models, the kinetic data for nitric acid decomposition reactions has been investigated in order to produce an initial dynamic model of decomposition under aqueous conditions. The identification of a set of kinetic reactions suitable for modelling has been the primary focus of this work. A model of nitric acid thermal decomposition will help develop a better understanding of nitric acid decomposition chemistry and enable better prediction of the oxidation states of species in solution. It is intended to later extend the model to include radiolytic reactions and then further to incorporate an organic phase in order to have a model which covers all decomposition routes for nitric acid within a nuclear fuel reprocessing scheme. The model will be used as a sub model for process models

Development of High Temperature Chemistry Measurement System for Establishment of On-Line Water Chemistry Surveillance Network in Nuclear Power Plant

International Nuclear Information System (INIS)

Yeon, Jei Won; Kim, Won Ho; Song, Kyu Seok; Joo, Ki Soo; Choi, Ke Chon; Ha, Yeong Keong; Ahn, Hong Joo; Im, Hee Jung; Maeng, Wan Young

2010-07-01

An integrated high-temperature water chemistry sensor (pH, E redox ) was developed for the establishment of the on-line water chemistry surveillance system in nuclear power plants. The basic performance of the integrated sensor was confirmed in high-temperature (280 .deg. C, 150kg/m 2 ) lithium borate solutions by using the relationship between the concentration of lithium ion and pH-E redox values. Especially, the effects of various environmental factors such as temperature, pressure, and flow rate on YSZ-based pH electrode were evaluated for ensuring the accuracy of high-temperature pH measurement. And the relationships between each water chemistry factor (pH, redox potential, electrical conductivity) were induced for enhancing the credibility of water chemistry measurement. In addition, on the basis of the evaluation of a nuclear plant design company, we suggested potential installation positions of the measurement system in a nuclear power plant

The Chemistry of Atmosphere-Forest Exchange (CAFE Model – Part 2: Application to BEARPEX-2007 observations

Directory of Open Access Journals (Sweden)

G. M. Wolfe

2011-02-01

Full Text Available In a companion paper, we introduced the Chemistry of Atmosphere-Forest Exchange (CAFE model, a vertically-resolved 1-D chemical transport model designed to probe the details of near-surface reactive gas exchange. Here, we apply CAFE to noontime observations from the 2007 Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX-2007. In this work we evaluate the CAFE modeling approach, demonstrate the significance of in-canopy chemistry for forest-atmosphere exchange and identify key shortcomings in the current understanding of intra-canopy processes.

CAFE generally reproduces BEARPEX-2007 observations but requires an enhanced radical recycling mechanism to overcome a factor of 6 underestimate of hydroxyl (OH concentrations observed during a warm (~29 °C period. Modeled fluxes of acyl peroxy nitrates (APN are quite sensitive to gradients in chemical production and loss, demonstrating that chemistry may perturb forest-atmosphere exchange even when the chemical timescale is long relative to the canopy mixing timescale. The model underestimates peroxy acetyl nitrate (PAN fluxes by 50% and the exchange velocity by nearly a factor of three under warmer conditions, suggesting that near-surface APN sinks are underestimated relative to the sources. Nitric acid typically dominates gross dry N deposition at this site, though other reactive nitrogen (NO_y species can comprise up to 28% of the N deposition budget under cooler conditions. Upward NO₂ fluxes cause the net above-canopy NO_y flux to be ~30% lower than the gross depositional flux. CAFE under-predicts ozone fluxes and exchange velocities by ~20%. Large uncertainty in the parameterization of cuticular and ground deposition precludes conclusive attribution of non-stomatal fluxes to chemistry or surface uptake. Model-measurement comparisons of vertical concentration gradients for several emitted species suggests that the lower canopy airspace may be

Contribution from philosophy of chemistry to chemistry education: In a case of ionic liquids as technochemistry

Science.gov (United States)

Mudzakir, Ahmad; Hernani, Widhiyanti, Tuszie; Sudrajat, Devi Pratiwi

2017-08-01

Traditional chemistry education is commonly handing down of concepts, principles, and theories, such as mechanical properties, the relationship between structure and properties as well as chemical structure and chemical bonding theory, to students without engaging them in the processes of chemical inquiry. This practice leads to the lack of opportunity for the students to construct an appropriate understanding of these concepts, principles, and theories. Students are also rarely facilitated in modeling the structure and function of matter themselves. This situation shows that the philosophy of chemistry has not received as much attention from chemistry educators. The main idea of this paper is to embed philosophy of chemistry through the implementation of technochemistry in chemistry education. One of the most interesting and rapidly developing areas of modern chemistry, technologies and engineering is Ionic Liquids (ILs) as an emerging knowledge on technochemistry which can be applied to chemistry education. The developments between academic researchers and industrial developments in the ILs area are conducted in parallel. In order to overcome the existing problems of scientific development in chemistry education, the science and technology of ILs can be used for reconceptualizing the teaching and learning of chemistry to embrace the epistemology in chemistry. This study promises a potential contribution by philosophy of chemistry. The main objectives of this study are to develop: (i) a perspective based on philosophy of science considerations (rational reconstruction) in order to understand ionic liquids and (ii) teaching materials that can be used to enhance pre-service teacher's view of nature of science and technology (VNOST). The method used in the study is analytical-descriptive (elementarization), i.e. the first step in the model of educational reconstruction (MER). This study concludes that the development of the concepts and their applications of ionic

Medicinal electrochemistry: integration of electrochemistry, medicinal chemistry and computational chemistry.

Science.gov (United States)

Almeida, M O; Maltarollo, V G; de Toledo, R A; Shim, H; Santos, M C; Honorio, K M

2014-01-01

Over the last centuries, there were many important discoveries in medicine that were crucial for gaining a better understanding of several physiological processes. Molecular modelling techniques are powerful tools that have been successfully used to analyse and interface medicinal chemistry studies with electrochemical experimental results. This special combination can help to comprehend medicinal chemistry problems, such as predicting biological activity and understanding drug action mechanisms. Electrochemistry has provided better comprehension of biological reactions and, as a result of many technological improvements, the combination of electrochemical techniques and biosensors has become an appealing choice for pharmaceutical and biomedical analyses. Therefore, this review will briefly outline the present scope and future advances related to the integration of electrochemical and medicinal chemistry approaches based on various applications from recent studies.

Indirect photopatterning of functionalized organic monolayers via copper-catalyzed "click chemistry"

Science.gov (United States)

Williams, Mackenzie G.; Teplyakov, Andrew V.

2018-07-01

Solution-based lithographic surface modification of an organic monolayer on a solid substrate is attained based on selective area photo-reduction of copper (II) to copper (I) to catalyze the azide-alkyne dipolar cycloaddition "click" reaction. X-ray photoelectron spectroscopy is used to confirm patterning, and spectroscopic results are analyzed and supplemented with computational models to confirm the surface chemistry. It is determined that this surface modification approach requires irradiation of the solid substrate with all necessary components present in solution. This method requires only minutes of irradiation to result in spatial and temporal control of the covalent surface functionalization of a monolayer and offers the potential for wavelength tunability that may be desirable in many applications utilizing organic monolayers.

The implications of non-linear nitrogen chemistry in the HARM Model for use by the Environment Agency

International Nuclear Information System (INIS)

Metcalfe, S.E.; Whyatt, J.D.

2000-03-01

The findings of research into the linearity of the oxidised nitrogen chemistry in the Hull Acid Rain Model are presented, The background and structure of the HARM model are presented with modelling results, conclusions and recommendations. (author)

Aerosols, Chemistry, and Radiative Forcing: A 3-D Model Analysis of Satellite and ACE-Asia data (ACMAP)

Science.gov (United States)

Chin, Mian; Ginoux, Paul; Torres, Omar; Zhao, Xue-Peng

2005-01-01

We propose a research project to incorporate a global 3-D model and satellite data into the multi-national Aerosol Characterization Experiment-Asia (ACE-Asia) mission. Our objectives are (1) to understand the physical, chemical, and optical properties of aerosols and the processes that control those properties over the Asian-Pacific region, (2) to investigate the interaction between aerosols and tropospheric chemistry, and (3) to determine the aerosol radiative forcing over the Asia-Pacific region. We will use the Georgia TecWGoddard Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) model to link satellite observations and the ACE-Asia measurements. First, we will use the GOCART model to simulate aerosols and related species, and evaluate the model with satellite and in-situ observations. Second, the model generated aerosol vertical profiles and compositions will be used to validate the satellite products; and the satellite data will be used for during- and post- mission analysis. Third, we will use the model to analyze and interpret both satellite and ACE- Asia field campaign data and investigate the aerosol-chemistry interactions. Finally, we will calculate aerosol radiative forcing over the Asian-Pacific region, and assess the influence of Asian pollution in the global atmosphere. We propose a research project to incorporate a global 3-D model and satellite data into

Implementation of a PETN failure model using ARIA's general chemistry framework

Energy Technology Data Exchange (ETDEWEB)

Hobbs, Michael L. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2017-01-01

We previously developed a PETN thermal decomposition model that accurately predicts thermal ignition and detonator failure [1]. This model was originally developed for CALORE [2] and required several complex user subroutines. Recently, a simplified version of the PETN decomposition model was implemented into ARIA [3] using a general chemistry framework without need for user subroutines. Detonator failure was also predicted with this new model using ENCORE. The model was simplified by 1) basing the model on moles rather than mass, 2) simplifying the thermal conductivity model, and 3) implementing ARIA’s new phase change model. This memo briefly describes the model, implementation, and validation.

Impact of aircraft emissions on the atmospheric chemistry

Energy Technology Data Exchange (ETDEWEB)

Dameris, M; Sausen, R; Grewe, V; Koehler, I; Ponater, M [Deutsche Forschungs- und Versuchsanstalt fuer Luft- und Raumfahrt e.V., Oberpfaffenhofen (Germany). Inst. fuer Physik der Atmosphaere; Steil, B [Max-Planck-Inst. fuer Meteorologie, Hamburg (Germany); Bruehl, Ch [Max-Planck-Inst. fuer Chemie (Otto-Hahn-Institut), Mainz (Germany)

1998-12-31

A hierarchy of models of different complexity has been applied to estimate the impact of aircraft NO{sub x} emissions on atmospheric chemistry. The global circulation model ECHAM3 has been coupled with two types of chemistry modules. The first of these describes only a simplified (linear) NO{sub x} and HNO{sub 3} chemistry while the second one is a comprehensive chemistry module (CHEM), describing tropospheric and stratospheric chemistry including photochemical reactions and heterogeneous reactions on sulphate aerosols and PSCs. The module CHEM has been coupled either off-line or with feedback via the ozone concentration. First results of multilayer integrations (over decades) are discussed. (author) 27 refs.

Impact of aircraft emissions on the atmospheric chemistry

Energy Technology Data Exchange (ETDEWEB)

Dameris, M.; Sausen, R.; Grewe, V.; Koehler, I.; Ponater, M. [Deutsche Forschungs- und Versuchsanstalt fuer Luft- und Raumfahrt e.V., Oberpfaffenhofen (Germany). Inst. fuer Physik der Atmosphaere; Steil, B. [Max-Planck-Inst. fuer Meteorologie, Hamburg (Germany); Bruehl, Ch. [Max-Planck-Inst. fuer Chemie (Otto-Hahn-Institut), Mainz (Germany)

1997-12-31

A hierarchy of models of different complexity has been applied to estimate the impact of aircraft NO{sub x} emissions on atmospheric chemistry. The global circulation model ECHAM3 has been coupled with two types of chemistry modules. The first of these describes only a simplified (linear) NO{sub x} and HNO{sub 3} chemistry while the second one is a comprehensive chemistry module (CHEM), describing tropospheric and stratospheric chemistry including photochemical reactions and heterogeneous reactions on sulphate aerosols and PSCs. The module CHEM has been coupled either off-line or with feedback via the ozone concentration. First results of multilayer integrations (over decades) are discussed. (author) 27 refs.

Exact solutions for some discrete models of the Boltzmann equation

International Nuclear Information System (INIS)

Cabannes, H.; Hong Tiem, D.

1987-01-01

For the simplest of the discrete models of the Boltzmann equation: the Broadwell model, exact solutions have been obtained by Cornille in the form of bisolitons. In the present Note, we build exact solutions for more complex models [fr

Multivariate Calibration and Model Integrity for Wood Chemistry Using Fourier Transform Infrared Spectroscopy

OpenAIRE

Zhou, Chengfeng; Jiang, Wei; Cheng, Qingzheng; Via, Brian K.

2015-01-01

This research addressed a rapid method to monitor hardwood chemical composition by applying Fourier transform infrared (FT-IR) spectroscopy, with particular interest in model performance for interpretation and prediction. Partial least squares (PLS) and principal components regression (PCR) were chosen as the primary models for comparison. Standard laboratory chemistry methods were employed on a mixed genus/species hardwood sample set to collect the original data. PLS was found to provide bet...

Proceedings of the specialists' workshop on iodine chemistry in reactor safety, September 11th and 12th, 1985 at AERE, Harwell, England

International Nuclear Information System (INIS)

Deane, A.M.; Potter, P.E.

1986-01-01

The iodine workshop, held at Harwell in Sept. 1985, provided a forum to study the chemistry of iodine under reactor accident conditions. The major issues discussed were iodine equilibrium and kinetics in aqueous solutions, radiolysis of iodine in aqueous solutions, iodine/boric acid reactions, organic iodine compounds and partition measurements. Other factors must be identified before a complete model of iodine behaviour during reactor accidents can be established. (U.K.)

SITE 94. Modelling of groundwater chemistry at Aespoe Hard Rock Laboratory

Energy Technology Data Exchange (ETDEWEB)

Emren, A.T. [Chalmers Univ. of Technology, Goeteborg (Sweden). Dept. of Nuclear Chemistry

1999-02-01

In this report a model is described, which has been able to give agreement between observed and modelled values for more than ten element concentrations (including pH and pE values). The model makes use of a number of steady state waters which are mixed naturally after which the mixtures react with minerals in the fractures. The end member waters are supposed to have been present in the fracture system during a time interval which is long enough for the rock groundwater system to have reached a steady state. Some elements, e.g. chlorine, is modelled as conservative (inert with respect to the rock). Most element concentrations cannot be explained from mixing alone. Rather reactions with the fracture walls have to be taken into account. The situation is complicated by the fact that a system comprised of groundwater and a number of fracture minerals may violate Gibb`s phase rule. In such a system, no global equilibrium state exists, and thus the water can never reach equilibrium with respect to all the fracture minerals. The end member waters eventually formed can be expected to be in a steady state condition rather than equilibrium with respect to the fracture minerals. It should be noted that such a steady state is not an equilibrium state. Rather, the water chemistry has to fluctuate as a result of spatial variability in the local mineral set. In most cases when an end member water is sampled, a large number of local waters are mixed causing the fluctuations to cancel out. The CRACKER is a program which has been developed to handle this complicated chemical situation. It couples chemistry and transport, using elaborate chemical modelling in combination with a simplified transport model. The program simulates chemical reactions of groundwater flowing through a plane fracture. The simulation results show that although the end member waters are far from equilibrium with respect to most of the minerals, they are in a steady state with respect to the rock. The chemistry

SITE 94. Modelling of groundwater chemistry at Aespoe Hard Rock Laboratory

International Nuclear Information System (INIS)

Emren, A.T.

1999-02-01

In this report a model is described, which has been able to give agreement between observed and modelled values for more than ten element concentrations (including pH and pE values). The model makes use of a number of steady state waters which are mixed naturally after which the mixtures react with minerals in the fractures. The end member waters are supposed to have been present in the fracture system during a time interval which is long enough for the rock groundwater system to have reached a steady state. Some elements, e.g. chlorine, is modelled as conservative (inert with respect to the rock). Most element concentrations cannot be explained from mixing alone. Rather reactions with the fracture walls have to be taken into account. The situation is complicated by the fact that a system comprised of groundwater and a number of fracture minerals may violate Gibb's phase rule. In such a system, no global equilibrium state exists, and thus the water can never reach equilibrium with respect to all the fracture minerals. The end member waters eventually formed can be expected to be in a steady state condition rather than equilibrium with respect to the fracture minerals. It should be noted that such a steady state is not an equilibrium state. Rather, the water chemistry has to fluctuate as a result of spatial variability in the local mineral set. In most cases when an end member water is sampled, a large number of local waters are mixed causing the fluctuations to cancel out. The CRACKER is a program which has been developed to handle this complicated chemical situation. It couples chemistry and transport, using elaborate chemical modelling in combination with a simplified transport model. The program simulates chemical reactions of groundwater flowing through a plane fracture. The simulation results show that although the end member waters are far from equilibrium with respect to most of the minerals, they are in a steady state with respect to the rock. The chemistry

Reaction Pathways in Catechol/Primary Amine Mixtures: A Window on Crosslinking Chemistry.

Directory of Open Access Journals (Sweden)

Juan Yang

Full Text Available Catechol chemistry is used as a crosslinking tool abundantly in both natural organisms (e.g. mussels, sandcastle worms and synthetic systems to achieve the desired mechanical properties. Despite this abundance and success, the crosslinking chemistry is still poorly understood. In this study, to simplify the system, yet to capture the essential chemistry, model compounds 4-methyl catechol and propylamine are used. The reaction of 4-methyl catechol (2 mM with propylamine (6 mM is carried out in the presence of NaIO4 (2 mM in 10 mM Na2CO3 aqueous solution. A variety of spectroscopic/spectrometric and chromatographic methods such as 1H NMR, LC-MS, and UV-VIS are used to track the reaction and identify the products/intermediates. It is found that the crosslinking chemistry of a catechol and an amine is both fast and complicated. Within five minutes, more than 60 products are formed. These products encompass 19 different masses ranging from molecular weight of 179 to 704. By combining time-dependent data, it is inferred that the dominant reaction pathways: the majority is formed via aryloxyl-phenol coupling and Michael-type addition, whereas a small fraction of products is formed via Schiff base reactions.

Classical solutions for the 4-dimensional σ-nonlinear model

International Nuclear Information System (INIS)

Tataru-Mihai, P.

1979-01-01

By interpreting the σ-nonlinear model as describing the Gauss map associated to a certain immersion, several classes of classical solutions for the 4-dimensional model are derived. As by-products one points out i) an intimate connection between the energy-momentum tensor of the solution and the second differential form of the immersion associated to it and ii) a connection between self- (antiself-)duality of the solution and the minimality of the associated immersion. (author)

Dimethylsulfide chemistry: annual, seasonal, and spatial impacts on SO_4^(2-)

Science.gov (United States)

We incorporated oceanic emissions and atmospheric chemistry of dimethylsulfide (DMS) into the hemispheric Community Multiscale Air Quality model and performed annual model simulations without and with DMS chemistry. The model without DMS chemistry predicts higher concentrations o...

A plant wide aqueous phase chemistry model describing pH variations and ion speciation/pairing in wastewater treatment process models

DEFF Research Database (Denmark)

Flores-Alsina, X.; Mbamba, C. Kazadi; Solon, K.

cationic/anionic loads. In this way, the general applicability/flexibility of the proposed approach is demonstrated by implementing the aqueous phase chemistry module in some of the most frequently used WWTP process simulation models. Finally, it is shown how traditional wastewater modelling studies can......, require a major, but unavoidable, additional degree of complexity when representing cationic/anionic behaviour in Activated Sludge (AS)/Anaerobic Digestion (AD) systems (Ikumi et al., 2014). In this paper, a plant-wide aqueous phase chemistry module describing pH variations plus ion speciation...... of Ordinary Differential Equations (ODEs) in order to reduce the overall stiffness of the system, thereby enhancing simulation speed. Additionally, a multi-dimensional version of the Newton-Raphson algorithm is applied to handle the existing multiple algebraic inter-dependencies (Solon et al., 2015...

Air traffic simulation in chemistry-climate model EMAC 2.41: AirTraf 1.0

Science.gov (United States)

Yamashita, Hiroshi; Grewe, Volker; Jöckel, Patrick; Linke, Florian; Schaefer, Martin; Sasaki, Daisuke

2016-09-01

Mobility is becoming more and more important to society and hence air transportation is expected to grow further over the next decades. Reducing anthropogenic climate impact from aviation emissions and building a climate-friendly air transportation system are required for a sustainable development of commercial aviation. A climate optimized routing, which avoids climate-sensitive regions by re-routing horizontally and vertically, is an important measure for climate impact reduction. The idea includes a number of different routing strategies (routing options) and shows a great potential for the reduction. To evaluate this, the impact of not only CO2 but also non-CO2 emissions must be considered. CO2 is a long-lived gas, while non-CO2 emissions are short-lived and are inhomogeneously distributed. This study introduces AirTraf (version 1.0) that performs global air traffic simulations, including effects of local weather conditions on the emissions. AirTraf was developed as a new submodel of the ECHAM5/MESSy Atmospheric Chemistry (EMAC) model. Air traffic information comprises Eurocontrol's Base of Aircraft Data (BADA Revision 3.9) and International Civil Aviation Organization (ICAO) engine performance data. Fuel use and emissions are calculated by the total energy model based on the BADA methodology and Deutsches Zentrum für Luft- und Raumfahrt (DLR) fuel flow method. The flight trajectory optimization is performed by a genetic algorithm (GA) with respect to a selected routing option. In the model development phase, benchmark tests were performed for the great circle and flight time routing options. The first test showed that the great circle calculations were accurate to -0.004 %, compared to those calculated by the Movable Type script. The second test showed that the optimal solution found by the algorithm sufficiently converged to the theoretical true-optimal solution. The difference in flight time between the two solutions is less than 0.01 %. The dependence of

Stability of subsystem solutions in agent-based models

Science.gov (United States)

Perc, Matjaž

2018-01-01

The fact that relatively simple entities, such as particles or neurons, or even ants or bees or humans, give rise to fascinatingly complex behaviour when interacting in large numbers is the hallmark of complex systems science. Agent-based models are frequently employed for modelling and obtaining a predictive understanding of complex systems. Since the sheer number of equations that describe the behaviour of an entire agent-based model often makes it impossible to solve such models exactly, Monte Carlo simulation methods must be used for the analysis. However, unlike pairwise interactions among particles that typically govern solid-state physics systems, interactions among agents that describe systems in biology, sociology or the humanities often involve group interactions, and they also involve a larger number of possible states even for the most simplified description of reality. This begets the question: when can we be certain that an observed simulation outcome of an agent-based model is actually stable and valid in the large system-size limit? The latter is key for the correct determination of phase transitions between different stable solutions, and for the understanding of the underlying microscopic processes that led to these phase transitions. We show that a satisfactory answer can only be obtained by means of a complete stability analysis of subsystem solutions. A subsystem solution can be formed by any subset of all possible agent states. The winner between two subsystem solutions can be determined by the average moving direction of the invasion front that separates them, yet it is crucial that the competing subsystem solutions are characterised by a proper composition and spatiotemporal structure before the competition starts. We use the spatial public goods game with diverse tolerance as an example, but the approach has relevance for a wide variety of agent-based models.

Equilibrium and kinetic models for colloid release under transient solution chemistry conditions

Science.gov (United States)

We present continuum models to describe colloid release in the subsurface during transient physicochemical conditions. Our modeling approach relates the amount of colloid release to changes in the fraction of the solid surface area that contributes to retention. Equilibrium, kinetic, equilibrium and...

Variational methods for direct/inverse problems of atmospheric dynamics and chemistry

Science.gov (United States)

Penenko, Vladimir; Penenko, Alexey; Tsvetova, Elena

2013-04-01

We present a variational approach for solving direct and inverse problems of atmospheric hydrodynamics and chemistry. It is important that the accurate matching of numerical schemes has to be provided in the chain of objects: direct/adjoint problems - sensitivity relations - inverse problems, including assimilation of all available measurement data. To solve the problems we have developed a new enhanced set of cost-effective algorithms. The matched description of the multi-scale processes is provided by a specific choice of the variational principle functionals for the whole set of integrated models. Then all functionals of variational principle are approximated in space and time by splitting and decomposition methods. Such approach allows us to separately consider, for example, the space-time problems of atmospheric chemistry in the frames of decomposition schemes for the integral identity sum analogs of the variational principle at each time step and in each of 3D finite-volumes. To enhance the realization efficiency, the set of chemical reactions is divided on the subsets related to the operators of production and destruction. Then the idea of the Euler's integrating factors is applied in the frames of the local adjoint problem technique [1]-[3]. The analytical solutions of such adjoint problems play the role of integrating factors for differential equations describing atmospheric chemistry. With their help, the system of differential equations is transformed to the equivalent system of integral equations. As a result we avoid the construction and inversion of preconditioning operators containing the Jacobi matrixes which arise in traditional implicit schemes for ODE solution. This is the main advantage of our schemes. At the same time step but on the different stages of the "global" splitting scheme, the system of atmospheric dynamic equations is solved. For convection - diffusion equations for all state functions in the integrated models we have developed the

OCEANFILMS-2: Representing coadsorption of saccharides in marine films and potential impacts on modeled marine aerosol chemistry

Energy Technology Data Exchange (ETDEWEB)

Burrows, Susannah M. [Atmospheric Science and Global Change Division, Pacific Northwest National Laboratory, Richland Washington USA; Gobrogge, Eric [Department of Chemistry and Biochemistry, Montana State University, Bozeman Montana USA; Fu, Li [Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland Washington USA; Link, Katie [Department of Chemistry and Biochemistry, Montana State University, Bozeman Montana USA; Elliott, Scott M. [Climate, Ocean, and Sea Ice Modelling Group, Los Alamos National Laboratory, Los Alamos New Mexico USA; Wang, Hongfei [Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland Washington USA; Walker, Rob [Department of Chemistry and Biochemistry, Montana State University, Bozeman Montana USA

2016-08-10

Here we show that the addition of chemical interactions of soluble polysaccharides with a surfactant monolayer improves agreement of modeled sea spray chemistry with observed marine aerosol chemistry. In particular, the fraction of hydroxyl functional groups in modeled sea spray organic matter is increased, improving agreement with FTIR observations of marine aerosol composition. The overall organic fraction of submicron sea spray also increases, allowing organic mass fractions in the range 0.5 – 0.7 for submicron sea spray particles over highly active phytoplankton blooms. We show results from Sum Frequency Generation (SFG) experiments that support the modeling approach, by demonstrating that soluble polysaccharides can strongly adsorb to a lipid monolayer via columbic interactions under appropriate conditions.

How well can global chemistry models calculate the reactivity of short-lived greenhouse gases in the remote troposphere, knowing the chemical composition

Science.gov (United States)

Prather, Michael J.; Flynn, Clare M.; Zhu, Xin; Steenrod, Stephen D.; Strode, Sarah A.; Fiore, Arlene M.; Correa, Gustavo; Murray, Lee T.; Lamarque, Jean-Francois

2018-05-01

We develop a new protocol for merging in situ measurements with 3-D model simulations of atmospheric chemistry with the goal of integrating these data to identify the most reactive air parcels in terms of tropospheric production and loss of the greenhouse gases ozone and methane. Presupposing that we can accurately measure atmospheric composition, we examine whether models constrained by such measurements agree on the chemical budgets for ozone and methane. In applying our technique to a synthetic data stream of 14 880 parcels along 180° W, we are able to isolate the performance of the photochemical modules operating within their global chemistry-climate and chemistry-transport models, removing the effects of modules controlling tracer transport, emissions, and scavenging. Differences in reactivity across models are driven only by the chemical mechanism and the diurnal cycle of photolysis rates, which are driven in turn by temperature, water vapor, solar zenith angle, clouds, and possibly aerosols and overhead ozone, which are calculated in each model. We evaluate six global models and identify their differences and similarities in simulating the chemistry through a range of innovative diagnostics. All models agree that the more highly reactive parcels dominate the chemistry (e.g., the hottest 10 % of parcels control 25-30 % of the total reactivities), but do not fully agree on which parcels comprise the top 10 %. Distinct differences in specific features occur, including the spatial regions of maximum ozone production and methane loss, as well as in the relationship between photolysis and these reactivities. Unique, possibly aberrant, features are identified for each model, providing a benchmark for photochemical module development. Among the six models tested here, three are almost indistinguishable based on the inherent variability caused by clouds, and thus we identify four, effectively distinct, chemical models. Based on this work, we suggest that water vapor

The Role of Water Chemistry in Marine Aquarium Design: A Model System for a General Chemistry Class

Science.gov (United States)

Keaffaber, Jeffrey J.; Palma, Ramiro; Williams, Kathryn R.

2008-01-01

Water chemistry is central to aquarium design, and it provides many potential applications for discussion in undergraduate chemistry and engineering courses. Marine aquaria and their life support systems feature many chemical processes. A life support system consists of the entire recirculation system, as well as the habitat tank and all ancillary…

Applications, benefits and challenges of flow chemistry

DEFF Research Database (Denmark)

Mitic, Aleksandar; Heintz, Søren; Ringborg, Rolf Hoffmeyer

2013-01-01

, environmental and manufacturing perspective. A potential solution to resolve these issues is to use flow chemistry in such processes, preferably with applications of micro-and mini-sized equipment. In addition, Process Analytical Technology (PAT) may be implemented in a very efficient way in such equipment due...

Quantum Chemistry, and Eclectic Mix: From Silicon Carbide to Size Consistency

Energy Technology Data Exchange (ETDEWEB)

Rintelman, Jamie Marie [Iowa State Univ., Ames, IA (United States)

2004-12-19

Chemistry is a field of great breadth and variety. It is this diversity that makes for both an interesting and challenging field. My interests have spanned three major areas of theoretical chemistry: applications, method development, and method evaluation. The topics presented in this thesis are as follows: (1) a multi-reference study of the geometries and relative energies of four atom silicon carbide clusters in the gas phase; (2) the reaction of acetylene on the Si(100)-(2x1) surface; (3) an improvement to the Effective Fragment Potential (EFP) solvent model to enable the study of reactions in both aqueous and nonaqueous solution; and (4) an evaluation of the size consistency of Multireference Perturbation Theory (MRPT). In the following section, the author briefly discusses two topics central to, and present throughout, this thesis: Multi-reference methods and Quantum Mechanics/Molecular Mechanics (QM/MM) methods.

A Chemistry Concept Reasoning Test

Science.gov (United States)

Cloonan, Carrie A.; Hutchinson, John S.

2011-01-01

A Chemistry Concept Reasoning Test was created and validated providing an easy-to-use tool for measuring conceptual understanding and critical scientific thinking of general chemistry models and theories. The test is designed to measure concept understanding comparable to that found in free-response questions requiring explanations over…

Classical and Weak Solutions for Two Models in Mathematical Finance

Science.gov (United States)

Gyulov, Tihomir B.; Valkov, Radoslav L.

2011-12-01

We study two mathematical models, arising in financial mathematics. These models are one-dimensional analogues of the famous Black-Scholes equation on finite interval. The main difficulty is the degeneration at the both ends of the space interval. First, classical solutions are studied. Positivity and convexity properties of the solutions are discussed. Variational formulation in weighted Sobolev spaces is introduced and existence and uniqueness of the weak solution is proved. Maximum principle for weak solution is discussed.

Analytical chemistry: Principles and techniques

International Nuclear Information System (INIS)

Hargis, L.G.

1988-01-01

Although this text seems to have been intended for use in a one-semester course in undergraduate analytical chemistry, it includes the range of topics usually encountered in a two-semester introductory course in chemical analysis. The material is arranged logically for use in a two-semester course: the first 12 chapters contain the subjects most often covered in the first term, and the next 10 chapters pertain to the second (instrumental) term. Overall breadth and level of treatment are standards for an undergraduate text of this sort, and the only major omission is that of kinetic methods (which is a common omission in analytical texts). In the first 12 chapters coverage of the basic material is quite good. The emphasis on the underlying principles of the techniques rather than on specifics and design of instrumentation is welcomed. This text may be more useful for the instrumental portion of an analytical chemistry course than for the solution chemistry segment. The instrumental analysis portion is appropriate for an introductory textbook

Dial-A-Decon Solution Chemistry GAP Testing

Science.gov (United States)

2012-04-01

M25, Ml00, M250 , Ml000). The pipette size used was determined by the amount of extraction solution to be delivered. The analytical GC vials used...dilutions were prepared using Gilson Microman positive displacement pipettes (Gilson product numbers MIO, M25, Ml00, M250 , Ml000). The pipette size

Thermodynamic modelling of bentonite-groundwater interaction and implications for near field chemistry in a repository for spent fuel

International Nuclear Information System (INIS)

Wanner, H.; Wersin, P.; Sierro, N.

1992-11-01

Predictions of near field geochemistry are made using a thermodynamic model for bentonite/ground interaction. This model is a refinement and extension of the model developed by the senior author. It is based on recent experiments performed at high solid/water ratio and adapted to the Swedish type of HLW repository design. Thus, from the obtained experimental results on solution composition, the model includes chemical reactions resulting from both the impurities and the main clay fraction within the bentonite. Ion exchange reactions are treated both with and without the contribution of edge sites. Due to its thermodynamic basis, the model exhibits prediction capability over a wide range of conditions in terms of solid/water ratio. The modelling of repository conditions implies, due to the lack of experimental information, simplifications with regard to thermodynamic properties of the bentonite. This mainly involves the non-consideration of the temperature effects and of the acid/base properties of the solid. Nevertheless, our results yield insight into important processes affecting porewater chemistry. Thus, the model suggests that proton exchange reactions may exert a strong control on calcite dissolution within highly compacted bentonite. Estimations of chemical changes over time in the bentonite were done in the basis of a mixing tank model. These results indicate transformation of Na-bentonite to Ca-bentonite over time. The extent of this process, however, critically depends on the amount of carbonate present in the bentonite. (authors) (34 refs.)

Phenomenological modeling of combustion and NOx emissions using detailed tabulated chemistry methods in diesel engines

OpenAIRE

Rezaei, R.; Dinkelacker, F.; Tilch, B.; Delebinski, T.; Brauer, M.

2016-01-01

Enhancing the predictive quality of engine models, while maintaining an affordable computational cost, is of great importance. In this study, a phenomenological combustion and a tabulated NOx model, focusing on efficient modeling and improvement of computational effort, is presented. The proposed approach employs physical and chemical sub-models for local processes such as injection, spray formation, ignition, combustion, and NOx formation, being based on detailed tabulated chemistry methods....

The Fermi-Pasta-Ulam Model Periodic Solutions

CERN Document Server

Arioli, G; Terracini, S

2003-01-01

We introduce two novel methods for studying periodic solutions of the FPU beta-model, both numerically and rigorously. One is a variational approach, based on the dual formulation of the problem, and the other involves computer-assisted proofs. These methods are used e.g. to construct a new type of solutions, whose energy is spread among several modes, associated with closely spaced resonances.

Structure and chemistry of model catalysts in ultrahigh vacuum

Science.gov (United States)

Walker, Joshua D.

The study of catalysis is a key area of focus not only in the industrial sector but also in the nature and biological systems. The market for catalysis is a multi-billion dollar industry. Many of the materials and products we use on a daily basis are formed through a catalytic process. The quest to understanding and improving catalytic mechanisms is ongoing. Many model catalysts use transition metals as a support for chemical reactions to take place due to their selectivity and activity. Palladium, gold, and copper metals are studied in this work and show the ability to be catalytically reactive. It is important to understand the characteristics and properties of these surfaces. A well-known example of catalysis is the conversion of carbon monoxide (CO), a very harmful gas to carbon dioxide (CO2) which is less harmful. This reaction is mainly seen in the automotive industry. This reaction is investigated in this work on a Au(111) single crystal, which is normally inert but becomes reactivity with the adsorption of oxygen on the surface. Temperature Programmed Desorption (TPD) is used to understand some of the chemistry and effects with and without the addition of H2O. The oxidation of CO is shown to be enhanced by the addition of water, but warrants further analysis too fully understand the different mechanisms and reaction pathways existing. The field of nano-electronics is rapidly growing as technology continues to challenge scientists to create innovative ideas. The trend to produce smaller electronic products is increasing as consumer demands persist. It has been shown previously that 1,4-phenlyene diisocyanobenzene (1,4-PDI) on Au(111) react to form one-dimensional oligomer chains comprising alternating gold and 1,4-PDI units on the Au(111) surface. A similar compound 1,3-phenlyene diisocyanobenzene (1,3-PDI) was studied in order to investigate whether the oligomerization found for 1,4-PDI is a general phenomenon and to ultimately explore the effect of

Stepwise adsorption of phenanthrene at the fly ash-water interface as affected by solution chemistry: experimental and modeling studies.

Science.gov (United States)

An, Chunjiang; Huang, Guohe

2012-11-20

Fly ash (FA) is predominantly generated from coal-fired power plants. Contamination during disposal of FA can cause significant environmental problems. Knowledge about the interaction of FA and hydrophobic organic pollutants in the environment is very limited. This study investigated the adsorption of phenanthrene at the interface of FA and water. The performance of phenanthrene adsorption on FA and the effects of various aqueous chemistry conditions were evaluated. The adsorption isotherms exhibited an increasing trend in the adsorbed amounts of phenanthrene, while a stepwise pattern was apparent. A stepwise multisite Langmuir model was developed to simulate the stepwise adsorption process. The adsorption of phenanthrene onto FA was noted to be spontaneous at all temperatures. The thermodynamic results indicated that the adsorption was an exothermic process. The adsorption capacity gradually decreased as pH increased from 4 to 8; however, this trend became less significant when pH was changed from 8 to 10. The binding affinity of phenanthrene to FA increased after the addition of humic acid (HA). The pH variation was also responsible for the changes of phenanthrene adsorption on FA in the presence of HA. High ionic strength corresponded to low mobility of phenanthrene in the FA-water system. Results of this study can help reveal the migration patterns of organic contaminants in the FA-water system and facilitate environmental risk assessment at FA disposal sites.

PENGEMBANGAN MODEL PEMBELAJARAN KIMIA ANALITIK UNTUK MENINGKATKAN MUTU PENDIDIKAN GURU KIMIA

Directory of Open Access Journals (Sweden)

Mrs Liliasari

2015-01-01

Full Text Available The aim of the research is to improve chemistry teacher training program quality, use Analytical Chemistry Teaching Model (MPKA. The improvement should be on student higher order thinking skills. The model is consisting of 23 concepts, which include concepts that name process, concepts that have no perceptible instances, concepts which require knowledge of principles, concepts involving symbolic representation, formula and equation. Those concepts arrange in nine hierarchies on concept map. The model of teaching uses: (a concept and science process skill approach; (b problem solving and lecture method, and also laboratory activities; (c transparency and power point media; (d essay test. Critical thinking skills developed by the model are elementary clarification, basic support, inference and strategy and tactics. Creative thinking skills developed by the model are: (1 encouraging elegant solution of collision conflict, unsolved mysteries; (2 practicing the creative problem solving process in disciplined systematic manner in dealing with the problem and information at hand; (3 examining fantasies to find solution of real problems; (4 heightening anticipation only enough structure to give clues and direction. The model has been implemented to 82 students in three teacher’s training institutions (LPTK in Java and Bali. The model improves students’ comprehension in Chemistry concepts. It also develops three kinds of logics: group inclusion, proportional and combinatorial. Therefore it is suggested to develop similar models for other courses in perspectives chemistry teachers training program. Key words: Model of teaching, analytical chemistry, critical and creative thinking skills, quality improvement.

A comparison of atmospheric composition using the Carbon Bond and Regional Atmospheric Chemistry MechanismsChemistry Mechanisms

Science.gov (United States)

We incorporate the recently developed Regional Atmospheric Chemistry Mechanism (version 2, RACM2) into the Community Multiscale Air Quality modeling system for comparison with the existing 2005 Carbon Bond mechanism with updated toluene chemistry (CB05TU). Compared to CB05TU, RAC...

Pseudoclassical fermionic model and classical solutions

International Nuclear Information System (INIS)

Smailagic, A.

1981-08-01

We study classical limit of fermionic fields seen as Grassmann variables and deduce the proper quantization prescription using Dirac's method for constrained systems and investigate quantum meaning of classical solutions for the Thirring model. (author)

Problems and solutions in quantum chemistry and physics

CERN Document Server

Johnson, Charles S

1988-01-01

Unusually varied problems, with detailed solutions, cover quantum mechanics, wave mechanics, angular momentum, molecular spectroscopy, scattering theory, more. 280 problems, plus 139 supplementary exercises.

Radiative forcing estimates of sulfate aerosol in coupled climate-chemistry models with emphasis on the role of the temporal variability

Directory of Open Access Journals (Sweden)

C. Déandreis

2012-06-01

Full Text Available This paper describes the impact on the sulfate aerosol radiative effects of coupling the radiative code of a global circulation model with a chemistry-aerosol module. With this coupling, temporal variations of sulfate aerosol concentrations influence the estimate of aerosol radiative impacts. Effects of this coupling have been assessed on net fluxes, radiative forcing and temperature for the direct and first indirect effects of sulfate.

The direct effect respond almost linearly to rapid changes in concentrations whereas the first indirect effect shows a strong non-linearity. In particular, sulfate temporal variability causes a modification of the short wave net fluxes at the top of the atmosphere of +0.24 and +0.22 W m⁻² for the present and preindustrial periods, respectively. This change is small compared to the value of the net flux at the top of the atmosphere (about 240 W m⁻². The effect is more important in regions with low-level clouds and intermediate sulfate aerosol concentrations (from 0.1 to 0.8 μg (SO₄ m⁻³ in our model.

The computation of the aerosol direct radiative forcing is quite straightforward and the temporal variability has little effect on its mean value. In contrast, quantifying the first indirect radiative forcing requires tackling technical issues first. We show that the preindustrial sulfate concentrations have to be calculated with the same meteorological trajectory used for computing the present ones. If this condition is not satisfied, it introduces an error on the estimation of the first indirect radiative forcing. Solutions are proposed to assess radiative forcing properly. In the reference method, the coupling between chemistry and climate results in a global average increase of 8% in the first indirect radiative forcing. This change reaches 50% in the most sensitive regions. However, the reference method is not suited to run long climate

Importance of nuclear power for chemistry

International Nuclear Information System (INIS)

Kolotyrkin, J.

1982-01-01

Examples are given of the use of ionizing radiations in nuclear chemistry, in radiation cross-linking of polymers. The possibilities are also indicated of applications in the disinfection of wastes, in fertilizer production and packaging, in the production of cellulose and hydrogen. The implementation of the said technologies depends on the solution of a number organizational problems. (J.B.)

Effect of water chemistry on flow accelerated corrosion rate of carbon steel measured by on-line corrosion-monitoring system

International Nuclear Information System (INIS)

Fujiwara, K.; Domae, M.; Yoneda, K.; Inada, F.

2010-01-01

Flow Accelerated Corrosion (FAC) of carbon steel is one of the most important subjects in coolant systems of power plants. FAC is influenced by material, flow condition, temperature, and water chemistry. Iron and chromium solubility should be the most effective factor to determine the effect of water chemistry on the FAC. It is very important to evaluate the correlation between the solubility and the FAC rate of the carbon steel. In the present study, the effects of pH and Cr concentration of material on the FAC rate of carbon steel were evaluated by using high temperature loop equipment with on-line corrosion-monitoring system. Effect of dissolved oxygen concentration at pH 7 was also evaluated. The experimental FAC rates were compared with the calculation result, which was obtained from a FAC model developed previously by the authors' group. The tube specimens made of STPT 480 carbon steel were used for the FAC tests. The Cr concentration of STPT 480 was specially adjusted to 0.001 and 0.08 %. The inner diameters of the tubes were 1.6, 2.4, and 3.2 mm. The solutions were fed to the specimens with the flow rate of 1.5 l/min. The temperature of the solution at the specimen was controlled at 140 o C. Test solutions were demineralized water or NH 3 solutions of pH 8.0, 9.2, and 10.0. The increase in pH more than 9 decreased the FAC rates of both 0.001 and 0.08 % Cr specimens at 140 o C. Increase of the Cr concentration of the material decreased the FAC rate in the solution of pH 7.0, 8.0, 9.2, and 10.0. The FAC model reproduced well dependence of the experimental FAC behavior on water chemistry. It was confirmed that effect of pH and Cr concentration of material on the FAC rate were closely related to the solubility and diffusion of iron and chromium. (author)

Classical solutions for a one phase osmosis model

NARCIS (Netherlands)

Lippoth, F.; Prokert, G.

2011-01-01

For a moving boundary problem modelling the motion of a semipermeable membrane by osmotic pressure and surface tension we prove the existence and uniqueness of classical solutions on small time intervals. Moreover, we construct solutions existing on arbitrary long time intervals, provided the

Coupling between solute transport and chemical reactions models

International Nuclear Information System (INIS)

Samper, J.; Ajora, C.

1993-01-01

During subsurface transport, reactive solutes are subject to a variety of hydrodynamic and chemical processes. The major hydrodynamic processes include advection and convection, dispersion and diffusion. The key chemical processes are complexation including hydrolysis and acid-base reactions, dissolution-precipitation, reduction-oxidation, adsorption and ion exchange. The combined effects of all these processes on solute transport must satisfy the principle of conservation of mass. The statement of conservation of mass for N mobile species leads to N partial differential equations. Traditional solute transport models often incorporate the effects of hydrodynamic processes rigorously but oversimplify chemical interactions among aqueous species. Sophisticated chemical equilibrium models, on the other hand, incorporate a variety of chemical processes but generally assume no-flow systems. In the past decade, coupled models accounting for complex hydrological and chemical processes, with varying degrees of sophistication, have been developed. The existing models of reactive transport employ two basic sets of equations. The transport of solutes is described by a set of partial differential equations, and the chemical processes, under the assumption of equilibrium, are described by a set of nonlinear algebraic equations. An important consideration in any approach is the choice of primary dependent variables. Most existing models cannot account for the complete set of chemical processes, cannot be easily extended to include mixed chemical equilibria and kinetics, and cannot handle practical two and three dimensional problems. The difficulties arise mainly from improper selection of the primary variables in the transport equations. (Author) 38 refs

Third Chemistry Conference on Recent Trends in Chemistry

International Nuclear Information System (INIS)

Saeed, M.M.; Wheed, S.

2011-01-01

The third chemistry conference 2011 on recent trends in chemistry was held from October 17-19, 2001 at Islamabad, Pakistan. More than 65 papers and oral presentation. The scope of the conference was wide open and provides and opportunity for participation of broad spectrum of chemists. This forum provided a platform for the dissemination of the latest research followed by discussion pertaining to new trends in chemistry. This con fence covered different aspects of subjects including analytical chemistry, environmental chemistry, polymer chemistry, industrial chemistry, biochemistry and nano chemistry etc. (A.B.)

Effects of water chemistry and fluid dynamics on wall thinning behavior. Part 1. Development of FAC model focused on water chemistry and composition of material

International Nuclear Information System (INIS)

Fujiwara, Kazutoshi; Domae, Masafumi; Ohta, Joji; Yoneda, Kimitoshi; Inada, Fumio

2009-01-01

Flow Accelerated Corrosion (FAC), which is one of the important subjects at fossil and nuclear power plans, is caused by the accelerated dissolution of protective oxide film due to the turbulent flow. The influence factors on FAC such as water chemistry, material, and fluid dynamics are closely related to the oxide property so that the risk of FAC can be reduced by the suitable control of water chemistry. There are some FAC models and evaluation codes of FAC rate. Some of them are used in wall thinning management of nuclear power plant in some country. Nevertheless, these FAC codes include many empirical parameters so that some uncertainty to evaluate the synergistic effectiveness of factors are the controversial point for the application of FAC code to wall thinning management in Japanese nuclear power plant. In this study, a FAC model that can evaluate the effect of temperature, NH3 concentration, chromium content, and dissolved oxygen concentration on FAC rate was developed by considering the diffusion of dissolved species. The critical dissolved oxygen concentration, which can inhibit FAC, was also calculated by this model. (author)

A report on workshops: General circulation model study of climate- chemistry interaction

International Nuclear Information System (INIS)

Wei-Chyung, Wang; Isaksen, I.S.A.

1993-01-01

This report summarizes the discussion on General Circulation Model Study of Climate-Chemistry Interaction from two workshops, the first held 19--21 August 1992 at Oslo, Norway and the second 26--27 May 1993 at Albany, New York, USA. The workshops are the IAMAP activities under the Trace Constituent Working Group. The main objective of the two workshops was to recommend specific general circulation model (GCM) studies of the ozone distribution and the climatic effect of its changes. The workshops also discussed the climatic implications of increasing sulfate aerosols because of its importance to regional climate. The workshops were organized into four working groups: observation of atmospheric O 3 ; modeling of atmospheric chemical composition; modeling of sulfate aerosols; and aspects of climate modeling